Rewritable optical information recording medium, recording and reproducing methods, as well as recording and reproducing apparatus

ABSTRACT

A rewritable optical information recording medium including a recording layer composed of an organic dye film is provided, in which recording and erasing information can be performed reversibly by laser light irradiation. A rewritable optical information recording medium including at least one organic dye film which is substantially made of only at least one kind of organic dye compounds as a recording film is provided. The recording and erasure of information are performed by a reversible physical change of the organic dye film substance caused by laser light irradiation. Specifically, data recording is performed by a physical change locally caused by the irradiation of recording laser light, data reproduction is performed by detecting change in intensity of returned light of reproducing laser light having less power than the recording laser light, and data erasure is performed by applying at least once continuous light or pulse light having laser power more than the reproducing laser light and less than the recording laser light. The physical change is a change in shape.

TECHNICAL FIELD

The present invention relates to a novel rewritable optical informationrecording medium including a recording layer made of an organic dyefilm, in which recording and erasing of information can be reversiblyperformed by irradiating laser light, and further, to a recording andreproducing method as well as a recording and reproducing apparatus inwhich the medium is used.

BACKGROUND ART

Lately, as optical recording media widely used on the market, there arewrite-once organic optical discs (so-called CD-R, DVD-R and the like),rewritable phase change optical discs (so-called CD-RW, DVD-RW and thelike), and further, magneto optical discs and the like.

As regards the CD-RW and the DVD-RW, the phase change optical recordingmedium is made of a chalcogen-containing material such as Te—Ge—Sb alloyor Ag—In—Sb—Te alloy; however, these alloys are toxic. Moreover, adielectric film made of a sulfide, an oxide, or a nitride such as ZnS,ZnS—SiO₂, SiO₂, Si₃N₄, or AlN is required adjacent to a recording filmin order to induce phase change and form and erase a recorded markstably, and also a reflective film and the like made of Ag, Al, Agalloy, Al alloy, or the like is required in order to improve themodulation degree (contrast) of a recording signal and thermalcharacteristics. Since a vacuum deposition method such as a sputteringmethod or the like is required to form these thin films, and the filmstructure of a recording medium is complicated and the thickness of eachthin film must be controlled precisely, it is difficult to manufacturean inexpensive optical recording medium.

A magneto optical recording medium is conventionally made of an alloythin film consisting of a rare-earth element such as Gd or Tb and atransition metal such as Fe, Ni, Co, or the like; however, those alloythin films are easily oxidized by oxygen in moisture and in the air,etc. and therefore must be prevented from being exposed to the air by aprotective film such as SiO₂ or Si₃N₄, which shows the difficulty withrespect to the long-time recording stability. Also, since an externalmagnetic field is required for recording in theory, and further, theoptical Kerr effect is used for the reproduction principle of recordedinformation, there is a disadvantage with a complicated situation inwhich a polarizing optical system must be used.

On the other hand, a CD-R and DVD-R are optical recording media in whichrecording films are made of organic dye materials; however, they arewrite-once type media capable of writing only once and not rewritable.

Being capable of designing and synthesizing molecules, and also superiorin nontoxicity, cost performance and so forth as optical functionalmaterials, rewritable optical recording media made of organic materialsare being actively studied.

As rewritable optical recording media which use organic-based materials,photon mode type optical recording media and thermal mode (otherwisecalled heat mode) type optical recording media have so far beenreported.

For example, of the photon mode type, there are rewritable opticalrecording media utilizing the photochromism of fulgide, spiropyrane anddiarylethene. These rewritable optical recording media are described indetail in: Yasushi Yokoyama ‘Fulgides for Memories and Switches’, Chem.Rev. 2000, 100, 1717-1739; Garry Berkovic, ValeriKrongauz and VictorWeiss ‘Spiropyrans and Spirooxazines for Memories and Switches’, Chem.Rev. 2000, 100, 1741-1753; Masahiro Irie ‘Diarylethenes for Memories andSwitches’, Chem. Rev. 2000, 100, 1685-1716. However, in these opticalrecording media, different wavelength of laser light is used forrecording and reproduction, respectively.

In addition, since photochromic reaction is used in both recording andreproduction, light resistance with respect to reproducing light is low,and there are problems in stability and repeatability. Also, being ofphoton mode, those are highly sensitive and fast in speed but lacking inheat stability as well as in light resistance.

As a thermal mode type rewritable optical recording medium, the opticalrecording medium described in Japanese published unexamined patentapplication No. H6-60421, for example, is an optical recording medium,including a recording layer made of a shape-memory resin such aspolyurethane or a styrene-butadiene copolymer which contains a lightabsorbent such as inorganic or organic dye or color, in which a partrecorded by laser light rises to convexly protude due to thermalexpansion and then cools rapidly and hardens, and when erased, lighthaving power stronger than that at the time of recording is applied, orlaser light is applied for a longer period of time than at the time ofrecording. Also, in Japanese published patent application No. H6-1073,an optical recording medium which uses a recording layer containing aconjugated system polymer whose conformation changes according tothermal energy and dye which has light absorption power is described.

Also, in Japanese published patent application No. H9-226249,information rewriting executed by reversibly changing cohesive poweramong substituents of a central metal in a metal phthalocyanine compoundis proposed. Only an embodiment in which metal phthalocyanine compoundsare dissolved in high molecular compounds such as polystyrene andpolyamide is described.

Further, in Japanese published patent application No. H9-147414, anoptical recording medium utilizing an absorbance change of a recordinglayer, in which a recording layer is made of a photochromism orthermochromism material and an associative dye such as an azaannulenecompound, for example phthalocyanine, is proposed; however, onlyembodiments in which the above is mixed into high molecular compoundssuch as polystyrene and polymethyl methacrylate is described.

In all those examples, recording films in which organic dye having lightabsorption power is mixed dispersively into or is polymerized with highmolecular compounds are used, and the mixture ratio (or polymerizationratio) is 20-80%. In such cases, if the mixture ratio of light-absorbingdye dispersed in a system is low, the recording sensitivity diminishesbecause the amount of energy which is absorbed and converted to heat issmall, and it becomes difficult to get a large modulation degree becausethe proportion of dye is low. On the other hand, if the mixture ratio ishigh, agglutination, segregation, crystallization and association of dyeoccur unevenly, causing a signal noise. Also, unless an appropriate highmolecular compound or polymer is selected, there is a disadvantage inwhich the state of dispersion easily changes with time passed inpreservation, even if there is a uniform dispersion at the time ofdeposition. Further, regarding the process of making a disc, since it isnecessary to select a high molecular compound of a lowmoisture-absorption nature so as to gain stability in long-timepreservation, the downside is that selecting a solvent which dissolvesthis high molecular compound and also does not attack a substrate ofteninvolves difficulties of causing the insufficient repeatability.

Also, in Japanese patent No. 3054770, a method of causing change in thecrystallized state, involving reversible change in the orienteddirection of molecules, with respect to a recording layer made oforganic thin film-like crystals containing optical anisotropy such asfatty acid, a fatty acid derivative, a benzoic acid derivative, orn-alkane to detect differences in polarization characteristics isdescribed; however, the crystallinity degree of those organic thinfilm-like crystals is uneven, so that the signal noise level tends toincrease. Also, there is a problem in which a polarizing optical systemis required for a recording and reproducing apparatus similarly to thecase of a magneto optical disc.

It is necessary for an optical information recording medium to haveappropriate recording sensitivity capable of high density recording,good reproducing performance with low noise and high modulation degree,and superb rewriting performance with a high erasure ratio and allowingmany times of repetition; also in practice, it is important to have asimplified structure suitable for mass production. Further, it isdesirable for the optical information recording medium to havecompatibility with currently widespread optical recording media, such asa CD using a laser oscillation wavelength around 780 nm, a DVD usingthat of 650 nm or so, and also with the optical disc using a laseroscillation wavelength of 400 nm or so, which is considered to be anext-generation optical disc.

The present invention has been devised in light of the problems above,in which only organic dye thin film materials are employed as recordingfilms to also provide a rewritable optical information recording mediumand further, a recording and reproducing method and a recording andreproducing apparatus, which can satisfy the above-mentionedrequirements.

DISCLOSURE OF INVENTION

Conventionally, as organic dyes for a write-once type organic-basedoptical disc, such dyes as: polymethine-based dyes, that is,cyanine-based, azulene-based and squarylium-based dyes; metalcomplex-based dyes, that is, metal naphthalocyanine-based, metalphthalocyanine-based, porphyrin-based, azo-based, and indoaniline-baseddyes; quinone-based dyes, that is, anthraquinone-based andnaphthoquinone-based dyes; and the like have been studied and some ofthe above have partially been put into practical use. A write-once typeorganic optical disc with so-called the perforating mode as therecording principle was put into practical use in an early stage of thedevelopment.

As regards organic dye optical recording materials in CD-Rs and DVD-Rswidely used of late, the recording and reproducing principle is that anorganic dye recording film is thermally decomposed by energy locallyobtained by laser irradiation to change the optical constant thereof,and returning light (reflectance) of reproduction laser light is changedby phase modulation or amplitude modulation of the complex reflectance;and it is generally thought that rewriting is impossible.

The inventors of the present invention and others have found that theabove objectives can be achived by using an organic dye recording filmin which at least one of azaannulene compounds of less than 3000 inmolecular weight or of metal complexes thereof is used as an organicdye, which is not thermally decomposed when applying predetermined laserlight; and also by subjecting the film to physical change such asreversible deformation as simple organic dye substance without havingmixed or dispersed into high molecular compounds, with appropriatelyselecting irradiation conditions of beam light both at the time ofrecording and at the time of erasing.

The present invention is completed based on the above understandings.Specifically, a rewritable optical information recording mediumaccording to the present invention includes at least one layer of alight-absorbing organic compound film (organic dye film) substantiallycomposed of only at least one kind of light-absorbing organic compounds(including metal complexes thereof) (for example organic dye compounds)as a recording film, in which the recording and erasing of informationare performed by a reversible physical change (for example a change inshape such as deformation) of the organic dye film substance caused bylaser light irradiation. Further, a recording and reproducing methodaccording to the present invention is the method in which a rewritableoptical information recording medium including at least one layer of alight-absorbing organic compound film substantially composed of only atleast one kind of light-absorbing organic compounds (including metalcomplexes thereof) as a recording film, in which the recording anderasing of information are performed by a reversible physical change ofthe organic dye film substance caused by laser light irradiation.Further, a recording and reproducing apparatus according to the presentinvention is provided with a rewritable optical information recordingmedium including at least one layer of a light-absorbing organiccompound film substantially composed of only at least one kind oflight-absorbing organic compounds (including metal complexes thereof) asa recording film, in which the recording and erasing of information areperformed by a reversible physical change of the organic dye filmsubstance caused by laser light irradiation.

Recording on the information recording medium of the present inventionis performed by applying laser light corresponding to the absorptionwavelength of the above-mentioned light-absorbing organic compound (forexample organic dye) to heat and then rapidly cool the part irradiatedwith the laser light. As the laser light, it is preferable to use asmall-sized, lightweight semiconductor laser corresponding to theabsorption wavelength of the dye used. A part of an organic dye thinfilm in the recording layer, which is irradiated with the laser lightbecomes low in viscosity as the temperature rises; and by being bent orbocoming hollow in some cases due to expansion and contraction caused byfusion or sublimation, consequently the relevant part of the film isdeformed accompanied by a volume change or a mass transfer. In the caseof an optical disc in which a medium rotates at a high speed, afterlaser light is applied for a short period of time to heating, as soon asapplying the laser light is stopped the heated part is rapidly cooledwith ease when the laser spot passed. At this time, if the cooling rateis equal to or more than a certain critical cooling rate, the deformedpart is hardened to remain as the same shape, and thus becomes arecorded mark.

The reproduction of an information signal of the mark recorded in theabove-mentioned manner can be performed by applying light having lesspower than the light used at the times of recording and later-mentionederasure to detect the difference in the amount of returning light of therecorded portion and that of the unrecorded portion, similarly to thecases of the conventional CD-R and DVD-R. For example, if deformationcaused by hollowing-out occurs at the recorded mark, the value of theoptical constant of the hollow part stands approximately at n=1.0 andk=0.0 as a limit, even if a thermal decomposition reaction of organicdye does not occur, to be different from the value of the opticalconstant of the organic dye. Additionally, in the case accompanying adeformation such as a depression or protrusion caused by mass transferas well, the model in which the thickness of an organic dye recordingfilm locally changes at the recorded mark portion comes into effect, andsince its optical light path length (the recording layer's refractiveindex×film thickness) is locally changed, a phase change of incidentwave fronts of laser light occurs even when no change occurs in theabove optical constant, causing a reflectance change and a diffractionphenomenon, so that the amount of the returning light is modulated.Therefore, depending on the shape of grooves in the substrate, either ofthe amplitude modulation mode and the phase modulation mode can beselected, so that a sufficient modulation degree (contrast) can beobtained.

Further, erasure of recorded information, that is, the recorded mark canbe made by a method of heating the recorded portion and then graduallycooling it. The recorded portion or both the recorded and unrecordedportions may be heated by laser light irradiation. Accordingly, theerasure can be completed only by continuously scanning a track on whichinformation is recorded, with laser light having more power than thelaser light used on reproduction and less power than the laser lightused on recording. In the case of an optical disc in which a mediumrotates at a high speed, erasure can be executed by irradiating a trackon which the recorded mark has been made or a part of the track withcontinuous laser light at least once. If the erasing light is appliedcontinuously, the rate at which the recorded mark is cooled becomeslower than the above-mentioned critical cooling rate, which is referredto as slow cooling, a part in the vicinity of the laser spot of therecording film, whose temperature has risen, becomes low in viscosity,making mass transfer easily possible; and the deformed part isplanarized, eliminating a trace of the hollow part of the recorded mark,and is hardened again once it returns to its pre-recording shape.

Note that it is desirable for the required physical deformation to occurreversibly only in the recording layer made of organic dye, in terms ofits repeteted performance of recording, erasure, and recording. For thisreason, it is preferable that a trace of a plastic deformation does notremain on an interface adjacent to the dye layer, which is the recordinglayer.

However, it is difficult to conclude that the recording principle isdependent solely on deformation, and with respect to such submicronminute parts, detailed analysis will be necessary in the future; andthere is a possibility that some other physical changes such as changein the oriented state of organic dye molecules, phase change in thecrystallized state and conformation change might occur concurrently withdeformation. Altogether, to our surprise, we have found for the firsttime a rewritable optical recording medium in which reversible physicalchange of the above-mentioned organic dye film can be used.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic sectional view showing an example of a fundamentalstructure of a CD-R or DVD-R optical information recording medium;

FIG. 2 is a schematic sectional view showing another example of astructure of an optical information recording medium according to thepresent invention;

FIG. 3 is a schematic sectional view showing the fundamental structureof an optical information recording medium in which recording andreproduction are performed through a light-transmissive layer;

FIG. 4 is an explanatory drawing showing a calculation method of thereflectance of an optical recording medium, considering multiplereflection of light in a multilayer thin film;

FIG. 5 is a calculated example of the reflectance, according to thespecific structural example of FIG. 3;

FIG. 6 is a waveform chart showing a signal waveform (oscilloscopicimage) of initial recording according to an embodiment 1;

FIG. 7 is a waveform chart showing a signal waveform (oscilloscopicimage) after erasure was performed, according to the embodiment 1;

FIG. 8 is a waveform chart showing a signal waveform (oscilloscopicimage) at the time of re-recording, according to the embodiment 1;

FIG. 9 is a waveform chart showing a signal waveform (oscilloscopicimage) of initial recording, according to an embodiment 2;

FIG. 10 is a waveform chart showing a signal waveform (oscilloscopicimage) after erasure was performed, according to the embodiment 2;

FIG. 11 is a waveform chart showing a signal waveform (oscilloscopicimage) at the time of re-recording, according to the embodiment 2;

FIG. 12 is a waveform chart showing a signal waveform (oscilloscopicimage) after recording and erasure was carried out 20 timesrepetitively, according to the embodiment 2;

FIG. 13 is a waveform chart showing a signal waveform (oscilloscopicimage) of initial recording, according to an embodiment 3;

FIG. 14 is a waveform chart showing a signal waveform (oscilloscopicimage) after erasure was performed, according to the embodiment 3;

FIG. 15 is a waveform chart showing a signal waveform (oscilloscopicimage) at the time of re-recording, according to the embodiment 3;

FIG. 16 is a waveform chart showing an eye pattern (oscilloscopic image)of initial recording, according to the embodiment 3;

FIG. 17 is a schematic sectional view of an optical informationrecording medium of an embodiment 4;

FIG. 18 is a waveform chart showing a signal waveform (oscilloscopicimage) of initial recording, according to an embodiment 5;

FIG. 19 is a waveform chart showing a signal waveform (oscilloscopicimage) after erasure was performed, according to the embodiment 5;

FIG. 20 is a waveform chart showing a signal waveform (oscilloscopicimage) at the time of re-recording, according to the embodiment 5;

FIG. 21A is a photograph showing a deformation trace on the dye layerside when observing by SEM an exfoliated interface between a dielectriclayer on a substrate side and a dye layer, after recording wasperformed; FIG. 21B is a photograph showing a deformation trace on thedye layer side when observing by SEM an exfoliated interface between adielectric layer on the substrate side and a dye layer, after erasurewas performed; FIG. 21C is a photograph showing a deformation trace onthe dye layer side when observing by SEM an exfoliated interface betweena dielectric layer on the substrate side and a dye layer, afterre-recording was performed; and FIG. 21D is a photograph showing a SEMobservation image of the surface of a dielectric layer when observing bySEM an exfoliated interface between a dielectric layer on the substrateside and a dye layer, after recording was performed.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter embodiments of the present invention will be described. Itshould be noted that in the followings, as a recording medium,explanation will be made with respect to an optical disc in which, forexample, guide grooves, on these guide grooves a reflective film and arecording layer mainly composed of organic dye are formed on asubstrate, and recording and reproduction of a signal is performed byapplying blue-violet laser light of 350 to 450 nm in wavelength;however, the optical recording medium of the present invention is notlimited to the above shape and structure, and may be a card shape, sheetshape, or various kinds of other shapes; may have a structure without areflective layer; and to which recording and reproduction may beperformed using red laser light of 630 to 680 nm in wavelength,near-infrared laser light of 750 to 850 nm in wavelength, andshort-wavelength laser of 350 nm or less in wavelength as well.

As an example of an optical disc to which the present invention isapplied, FIG. 1 shows the one in which a substrate 1, a recording layer2, a reflective layer 3 and a protective film 4 are laminated in thisorder, and recording and reproduction are executed from the substrate 1side in the optical disc of FIG. 1. Other layers may exist between thesubstrate 1 and the recording layer 2, between the recording layer 2 andthe reflective layer 3, and between the reflective layer 3 and theprotective film 4; in an example of FIG. 2, transparent protective films5 and 6 are formed between the substrate 1 and the recording layer 2,and between the recording layer 2 and the reflective layer 3. Also, asanother embodiment, there is a structure of an optical disc in which therecording and reproduction of information are performed through alight-transmissive layer of 10 to 177 μm in thickness (hereinaftercalled DVR-Blue) (disclosed in Japanese published patent application No.H10-302310), for example the one, as shown in FIG. 3, in which areflective layer 2 and a recording layer 3 are deposited in this orderon a substrate 1 where guide grooves are formed, a light-transmissivelayer 8 is formed on this recording layer 3 with an arbitrarily formedtransparent protective film 7 in between, and the recording andreproduction of information are performed from the light-transmissivelayer 8 side. Considering the case in which the blue-violet laser lightis applied through the substrate 1 as shown in FIG. 1, a transparentmaterial, namely a polymeric material such as acrylic resin,polyethylene resin, polycarbonate resin, polyolefin resin, epoxy resin,etc. or an inorganic material such as glass, etc. is used for thesubstrate material, for example. On the other hand, as shown in thestructure in FIG. 3, if laser irradiation is performed from the side ofthe light-transmissive layer 8, which is opposite to the substrate 1side, it is not necessary for the substrate material to satisfy suchoptical requirements, so that it is possible to select the material froma wider range thereof. Materials capable of being injection molded, suchas acrylic resin, polycarbonate resin, polyolefin resin and the like arefavorable in terms of the mechanical characteristics required for thesubstrate and productivity. Guide grooves and/or pre-pits of 1 μm orless may be formed spirally or concentrically on the surface layers ofthose substrates. It is preferable that the guide grooves and pre-pitsbe provided when the substrate is formed, and those can be made byinjection molding using a stamper master, or by a thermal transfermethod using a photopolymer. Note that guide grooves and/or pre-pits maybe formed in the light-transmissive layer 8 in FIG. 3, and the samemanner can be used. For example, in the case of the DVR-Blue, it ispreferrable for the pitch and depth of the guide grooves to be selectedin the range of 0.2 to 0.80 μm for the pitch, and 20 to 150 nm for thedepth.

Materials constituting the recording layer in the optical recordingmedium of the present invention must have sufficient absorbency in thelaser wavelength band that is paid attention to, for example theoscillation wavelength band of a semiconductor laser loaded in therecording and reproducing apparatus used, and must locally heat therecording film with irradiating laser light having predetermined energy.Light-absorbing organic compounds described in the present invention arecompounds which absorb light; preferably organic compounds which causelight absorption, light emission, chemical and physical changes, etc.,interacting with light in the range of 180 to 2000 nm in wavelength,which are used as materials satisfying the above-mentioned conditions.As the light-absorbing organic compounds, organic dye compounds,particularly ones which interact with light in the range of wavelengthof ultraviolet light, visible light, and/or near-infrared light(preferably ultraviolet light, visible light, and/or near-infrared lightin the range of 350 nm to 850 nm in wavelength) are favorably used.

Specifically, examples of organic dye compounds of the present inventionused for optical recording media of the present invention whererecording is performed in oscillation wavelength bands of a blue-violetnitride-based semiconductor laser 350 to 450 nm in wavelength, of thered semiconductor laser 600 to 650 nm in wavelength used for the DVD-R,and of the near-infrared semiconductor laser 750 to 850 nm in wavelengthused for the CD-R can preferably be found in the followings: azaannulenecompounds; azaporphyrin compounds such as phthalocyanine,naphthalocyanine, tetraazaporphyrin, triazaporphyrin, diazaporphyrin andmonoazaporphyrin; metal complexes of porphyrin compounds and the like;and mixtures of two or more out of those compounds.

Azaannulene compounds described in the present invention are such cyclichydrocarbon compounds formed by conjugate double bonds, each includingat least one azaannulene ring where at least one of the carbon atomsconstituting the ring has been substituted by a nitrogen atom; and thepresent invention includes compounds complexed with metal atoms and/ormetalloid atoms. Also, a plurality of azaannulene rings may bond to eachother through one or more connecting radicals. As favorable examples ofcompounds, azaporphyrin-based compounds including phthalocyanine rings,naphthalocyanine rings, subphthalocyanine rings, monoazaporphyrin rings,diazaporphyrin rings, triazaporphyrin rings, tetraazaporphyrin rings, orthe like; and (aza) porphyrin compounds and the like, including pyrrolering structure, such as porphyrin-based compounds, etc. can bementioned. Each pyrrole ring in those ring structures may have acondensed ring; and substituents on the pyrrole rings and/or thecondensed rings may bond to each other through connecting radicals. Asexamples of condensed compounds, compounds whose benzene rings have beencondensed, such as dibenzotetraazaporphyrin compounds, phthalocyaninecompounds, and naphthalocyanine compounds, for example and the like canbe taken. Additionally, as other examples of compounds, compounds havingazaannulene rings that include structures where pyrrole rings in thering structure are directly single-bonded to each another, such asporphycene rings and corrole rings, can be taken, for example.

Azaannulene compounds used in the present invention are preferably:compounds having monomeric structures, in which bivalent metal atomswhich may have ligands, or trivalent to tetravalent metal/metalloidatoms which have substituents and/or ligands are coordinated; andcompounds having in their molecules dimeric structures, in which twoazaannulene rings bond to one metal atom having a central metal atom oftrivalent to tetravalent. Azaannulene compounds used in the presentinvention also include trimeric and multimeric structures. Sinceazaannulene compounds of less than 3000 in molecular weight which may bemetal complexes are in particular capable of arbitrarily selectingabsorption wavelengths thereof with their light absorption coefficientsbeing maintained by selecting substituents, those compounds areinvaluable organic dyes which can satisfy optical constants necessaryfor the recording layer in the aforementioned wavelengths of the laserlight.

Hereinafter, compounds for the recording layer described in the presentinvention will be explained in detail.

As azaannulene compounds in the present invention, compounds illustratedby General Formula (1) can be used as favorable examples.

[In the formula, R¹ to R¹⁶ each show individually a hydrogen atom, ahalogen atom, a nitro group, a cyano group, a substituted orunsubstituted hydrocarbon radical, a substituted or unsubstitutedhydroxyl group, a substituted or unsubstituted mercapto group, or asubstituted or unsubstituted amino group; X¹ to X⁸ each showindividually a nitrogen atom, or a substituted or unsubstituted methinegroup; substituents in R¹ to R¹⁶ and in methine groups may bond to eachother through a connecting radical; and there may be contained oxygenatoms, substituted or unsubstituted sulfur atoms and substituted orunsubstituted nitrogen atoms between carbon atoms in substituted orunsubstituted hydrocarbon radicals, in hydrocarbon-substituted hydroxylgroups, in hydrocarbon-substituted mercapto groups and/orhydrocarbon-substituted amino groups. Also, n represents 0 or 1; when nis 0, M represents a bivalent metal atom which may have a ligand, or atrivalent or tetravalent metal/metalloid atom which has a substituentand/or ligand, and when n is 1, M represents a trivalent metal atom andone hydrogen atom, or a tetravalent metal atom.]

As regards compounds shown by General Formula (1) of the presentinvention, a hydrogen atom; a halogen atom such as a fluorine atom, achlorine atom, a bromine atom, an iodine atom, etc.; a nitro group; acyano group; or the like can be mentioned as each of specific examplesof R¹ to R¹⁶

As specific examples of substituted or unsubstituted hydrocarbonradicals shown by R¹ to R¹⁶; substituted or unsubstituted alkyl groups,aralkyl groups, aryl groups, alkenyl groups and the like; which may haveoxygen atoms, substituted or unsubstituted sulfur atoms, and substitutedor unsubstituted nitrogen atoms between carbon atoms in the hydrocarbonradicals; can be mentioned.

The substituted or unsubstituted alkyl groups used for R¹ to R¹⁶ are:unsubstituted normal chain, branched-chain or cyclic alkyl groups of 1to 15 in carbon number, such as methyl group, ethyl group, n-propylgroup, iso-propyl group, n-butyl group, iso-butyl group, sec-butylgroup, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutylgroup, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group,1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group,4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group,1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group,1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutylgroup, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group,1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutylgroup, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group,2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group,5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group,2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentylgroup, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group,3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctylgroup, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group,1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctylgroup, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecylgroup, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptylgroup, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group,1-cyclopentyl-2,2-dimethylpropyl group and1-cyclohexyl-2,2-dimethylpropyl group;

halogen-substituted alkyl groups of 1 to 10 in carbon number, such aschloromethyl group, chloroethyl group, bromoethyl group, iodoethylgroup, dichloromethyl group, fluoromethyl group, trifluoromethyl group,pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethylgroup, 1,1,1,3,3,3-hexafluoro-2-propyl group, nonafluorobutyl group andperfluorodecyl group;

hydroxyl-substituted alkyl groups of 1 to 10 in carbon number, such ashydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group,4-hydroxybutyl group, 2-hydroxy-3-methoxypropyl group,2-hydroxy-3-chloropropyl group, 2-hydroxy-3-ethoxypropyl group,3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-cyclohexyloxypropyl group,2-hydroxypropyl group, 2-hydroxybutyl group and 4-hydroxydecalyl group;

hydroxyalkoxy-substituted alkyl groups of 2 to 10 in carbon number, suchas hydroxymethoxymethyl group, hydroxyethoxyethyl group,2-(2′-hydroxy-1′-methylethoxy)-1-methylethyl group,2-(3′-fluoro-2′-hydroxypropoxy)ethyl group,2-(3′-chloro-2′-hydroxypropoxy)ethyl group and hydroxybutoxycyclohexylgroup;

hydroxyalkoxyalkoxy-substituted alkyl groups of 3 to 10 in carbonnumber, such as hydroxymethoxymethoxymethyl group,hydroxyethoxyethoxyethyl group,[2′-(2′-hydroxy-1′-methylethoxy)-1′-methylethoxy]ethoxyethyl group,[2′-(2′-fluoro-1′-hydroxyethoxy)-1′-methylethoxy]ethoxyethyl group and[2′-(2′-chloro-1′-hydroxyethoxy)-1′-methylethoxy] ethoxyethyl group;

cyano-substituted alkyl groups of 2 to 10 in carbon number, such ascyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutylgroup, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group,2-cyano-3-ethoxypropyl group, 3-butoxy-2-cyanopropyl group,2-cyano-3-cyclohexylpropyl group, 2-cyanopropyl group and 2-cyanobutylgroup;

alkoxy-substituted alkyl groups of 2 to 15 in carbon number, such asmethoxymethyl group, ethoxymethyl group, propoxymethyl group,butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethylgroup, butoxyethyl group, n-hexyloxyethyl group, (4-methylpentoxy)ethylgroup, (1,3-dimethylbutoxy)ethyl group, (2-ethylhexyloxy)ethyl group,n-octyloxyethyl group, (3,5,5-trimethylhexyloxy)ethyl group,(2-methyl-1-iso-propylpropoxy)ethyl group,(3-methyl-1-iso-propylbutyloxy)ethyl group, 2-ethoxy-1-methylethylgroup, 3-methoxybutyl group, (3,3,3-trifluoropropoxy)ethyl group and(3,3,3-trichloropropoxy)ethyl group;

alkoxyalkoxy-substituted alkyl groups of 3 to 15 in carbon number, suchas methoxymethoxymethyl group, methoxyethoxyethyl group,ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethylgroup, cyclohexyloxyethoxyethyl group, decalyloxypropoxyethoxy group,(1,2-dimethylpropoxy)ethoxyethyl group,(3-methyl-1-iso-butylbutoxy)ethoxyethyl group,(2-methoxy-1-methylethoxy)ethyl group, (2-butoxy-1-methylethoxy)ethylgroup, 2-(2′-ethoxy-1′-methylethoxy)-1-methylethyl group,(3,3,3-trifluoropropoxy)ethoxyethyl group and(3,3,3-trichloropropoxy)ethoxyethyl group;

alkoxyalkoxyalkoxy-substituted alkyl groups of 4 to 15 in carbon number,such as methoxymethoxymethoxymethyl group, methoxyethoxyethoxyethylgroup, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group,cyclohexyloxyethoxyethoxyethyl group, propoxypropoxypropoxyethyl group,(2,2,2-trifluoroethoxy)ethoxyethoxyethyl group and(2,2,2-trichloroethoxy)ethoxyethoxyethyl group;

acyl-substituted alkyl groups of 2 to 10 in carbon number, such asformylmethyl group, 2-oxobutyl group, 3-oxobutyl group, 4-oxobutylgroup, 2,6-dioxocyclohexane-1-yl group and2-oxo-5-t-butylcyclohexane-1-1-yl group;

acyloxy-substituted alkyl groups of 2 to 15 in carbon number, such asformyloxymethyl group, acetoxyethyl group, propionyloxyethyl group,butanoyloxyethyl group, valeryloxyethyl group, (2-ethylhexanoyloxy)ethylgroup, (3,5,5-trimethylhexanoyloxy)ethyl group,(3,5,5-trimethylhexanoyloxy)hexyl group, (3-fluorobutyryloxy)ethyl groupand (3-chlorobutyryloxy)ethyl group;

acyloxyalkoxy-substituted alkyl groups of 3 to 15 in carbon number, suchas formyloxymethoxymethyl group, acetoxyethoxyethyl group,propionyloxyethoxyethyl group, valeryloxyethoxyethyl group,(2-ethylhexanoyloxy)ethoxyethyl group,(3,5,5-trimethylhexanoyl)oxybutoxyethyl group,(3,5,5-trimethylhexanoyloxy)ethoxyethyl group,(2-fluoropropionyloxy)ethoxyethyl group and(2-chloropropionyloxy)ethoxyethyl group;

acyloxyalkoxyalkoxy-substituted alkyl groups of 5 to 15 in carbonnumber, such as acetoxymethoxymethoxymethyl group,acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group,valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy)ethoxyethoxyethylgroup, (3,5,5-trimethylhexanoyloxy)ethoxyethoxyethyl group,(2-fluoropropionyloxy)ethoxyethoxyethyl group and(2-chloropropionyloxy)ethoxyethoxyethyl group;

alkoxycarbonyl-substituted alkyl groups of 3 to 15 in carbon number,such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group,butoxycarbonylmethyl group, methoxycarbonylethyl group,ethoxycarbonylethyl group, butoxycarbonylethyl group,(p-ethylcyclohexyloxycarbonyl)cyclohexyl group,(2,2,3,3,-tetrafluoropropoxycarbonyl)methyl group and(2,2,3,3-tetrachloropropoxycarbonyl)methyl group;

aryloxycarbonyl-substituted alkyl groups of 8 to 15 in carbon number,such as phenoxycarbonylmethyl group, phenoxycarbonylethyl group,(4-t-butylphenoxycarbonyl)ethyl group, naphthyloxycarbonylmethyl groupand biphenyloxycarbonylethyl group;

aralkyloxycarbonyl-substituted alkyl groups of 9 to 15 in carbon number,such as benzyloxycarbonylmethyl group, benzyloxycarbonylethyl group,phenethyloxycarbonylmethyl group and(4-cyclohexyloxybenzyloxycarbonyl)methyl group;

alkenyloxycarbonyl-substituted alkyl groups of 4 to 10 in carbon number,such as vinyloxycarbonylmethyl group, vinyloxycarbonylethyl group,allyloxycarbonylmethyl group, cyclopentadienyloxycarbonylmethyl groupand octenoxycarbonylmethyl group;

alkoxycarbonyloxy-substituted alkyl groups of 3 to 15 in carbon number,such as methoxycarbonyloxymethyl group, methoxycarbonyloxyethyl group,ethoxycarbonyloxyethyl group, butoxycarbonyloxyethyl group,(2,2,2-trifluoroethoxycarbonyloxy)ethyl group and(2,2,2-trichloroethoxycarbonyloxy)ethyl group;

alkoxyalkoxycarbonyloxy-substituted alkyl groups of 4 to 15 in carbonnumber, such as methoxymethoxycarbonyloxymethyl group,methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group,butoxyethoxycarbonyloxyethyl group,(2,2,2-trifluoroethoxy)ethoxycarbonyloxyethyl group and(2,2,2-trichloroethoxy)ethoxycarbonyloxyethyl group;

dialkylamino-substituted alkyl groups of 3 to 20 in carbon number, suchas dimethylaminomethyl group, diethylaminomethyl group,di-n-butylaminomethyl group, di-n-hexylaminomethyl group,di-n-octylaminomethyl group, di-n-decylaminomethyl group,N-isoamyl-N-methylaminomethyl group, piperidinomethyl group,di(methoxymethyl)aminomethyl group, di(methoxyethyl)aminomethyl group,di(ethoxymethyl)aminomethyl group, di(ethoxyethyl)aminomethyl group,di(propoxyethyl)aminomethyl group, di(butoxyethyl)aminomethyl group,bis(2-cyclohexyloxyethyl)aminomethyl group, dimethylaminoethyl group,diethylaminoethyl group, di-n-butylaminoethyl group,di-n-hexylaminoethyl group, di-n-octylaminoethyl group,di-n-decylaminoethyl group, N-isoamyl-N-methylaminoethyl group,piperidinoethyl group, di (methoxymethyl) aminoethyl group,di(methoxyethyl)aminoethyl group, di(ethoxymethyl)aminoethyl group,di(ethoxyethyl)aminoethyl group, di(propoxyethyl)aminoethyl group,di(butoxyethyl)aminoethyl group, bis(2-cyclohexyloxyethyl)aminoethylgroup, dimethylaminopropyl group, diethylaminopropyl group,di-n-butylaminopropyl group, di-n-hexylaminopropyl group,di-n-octylaminopropyl group, di-n-decylaminopropyl group,N-isoamyl-N-methylaminopropyl group, piperidinopropyl group,di(methoxymethyl)aminopropyl group, di(methoxyethyl)aminopropyl group,di(ethoxymethyl)aminopropyl group, di(ethoxyethyl)aminopropyl group,di(propoxyethyl)aminopropyl group, di(butoxyethyl)aminopropyl group,bis(2-cyclohexyloxyethyl)aminopropyl group, dimethylaminobutyl group,diethylaminobutyl group, di-n-butylaminobutyl group,di-n-hexylaminobutyl group, di-n-octylaminobutyl group,di-n-decylaminobutyl group, N-isoamyl-N-methylaminobutyl group,piperidinobutyl group, di (methoxymethyl) aminobutyl group,di(methoxyethyl)aminobutyl group, di(ethoxymethyl)aminobutyl group,di(ethoxyethyl)aminobutyl group, di(propoxyethyl)aminobutyl group,di(butoxyethyl)aminobutyl group and bis(2-cyclohexyloxyethyl)aminobutylgroup;

acylamino-substituted alkyl groups of 3 to 10 in carbon number, such asacetylaminomethyl group, acetylaminoethyl group, propionylaminoethylgroup, butanoylaminoethyl group, cyclohexanecarbonylaminoethyl group,p-methylcyclohexanecarbonylaminoethyl group and succiniminoethyl group;

alkylsulfonamino-substituted alkyl groups of 2 to 10 in carbon number,such as methylsulfonaminomethyl group, methylsulfonaminoethyl group,ethylsulfonaminoethyl group, propylsulfonaminoethyl group andoctylsulfonaminoethyl group;

alkylsulfonyl-substituted alkyl groups of 2 to 10 in carbon number, suchas methylsulfonylmethyl group, ethylsulfonylmethyl group,butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethylgroup, butylsulfonylethyl group, 2-ethylhexylsulfonylethyl group,2,2,3,3-tetrafluoropropylsulfonylmethyl group and2,2,3,3-tetrachloropropylsulfonylmethyl group;

arylsulfonyl-substituted alkyl groups of 7 to 12 in carbon number, suchas benzenesulfonylmethyl group, benzenesulfonylethyl group,benzenesulfonylpropyl group, benzenesulfonylbutyl group,toluenesulfonylmethyl group, toluenesulfonylethyl group,toluenesulfonylpropyl group, toluenesulfonylbutyl group,xylenesulfonylmethyl group, xylenesulfonylethyl group,xylenesulfonylpropyl group and xylenesulfonylbutyl group;

heterocycle-substituted alkyl groups of 2 to 13 in carbon number, suchas thiadiazolinomethyl group, pyrrolinomethyl group, pyrrolidinomethylgroup, pyrazolidinomethyl group, imidazolidinomethyl group, oxazolylgroup, triazolinomethyl group, morpholinomethyl group, indolinomethylgroup, benzimidazolinomethyl group and carbazolinomethyl group;

metallocenyl-substituted alkyl groups of 11 to 20 in carbon number, suchas ferrocenylmethyl group, ferrocenylethyl group, ferrocenyl-n-propylgroup, ferrocenyl-iso-propyl group, ferrocenyl-n-butyl group,ferrocenyl-iso-butyl group, ferrocenyl-sec-butyl group,ferrocenyl-t-butyl group, ferrocenyl-n-pentyl group,ferrocenyl-iso-pentyl group, ferrocenyl-2-methylbutyl group,ferrocenyl-1-methylbutyl group, ferrocenylneopentyl group,ferrocenyl-1,2-dimethylpropyl group, ferrocenyl-1,1-dimethylpropylgroup, ferrocenylcyclopentyl group, ferrocenyl-n-hexyl group,ferrocenyl-4-methylpentyl group, ferrocenyl-3-methylpentyl group,ferrocenyl-2-methylpentyl group, ferrocenyl-1-methylpentyl group,ferrocenyl-3,3-dimethylbutyl group, ferrocenyl-2,3-dimethylbutyl group,ferrocenyl-1,3-dimethylbutyl group, ferrocenyl-2,2-dimethylbutyl group,ferrocenyl-1,2-dimethylbutyl group, ferrocenyl-1,1-dimethylbutyl group,ferrocenyl-3-ethylbutyl group, ferrocenyl-2-ethylbutyl group,ferrocenyl-1-ethylbutyl group, ferrocenyl-1,2,2-trimethylbutyl group,ferrocenyl-1,1,2-trimethylbutyl group, ferrocenyl-1-ethyl-2-methylpropylgroup, ferrocenylcyclohexyl group, ferrocenyl-n-heptyl group,ferrocenyl-2-methylhexyl group, ferrocenyl-3-methylhexyl group,ferrocenyl-4-methylhexyl group, ferrocenyl-5-methylhexyl group,ferrocenyl-2,4-dimethylpentyl group, ferrocenyl-n-octyl group,ferrocenyl-2-ethylhexyl group, ferrocenyl-2,5-dimethylhexyl group,ferrocenyl-2,5,5-trimethylpentyl group, ferrocenyl-2,4-dimethylhexylgroup, ferrocenyl-2,2,4-trimethylpentyl group,ferrocenyl-3,5,5-trimethylhexyl group, ferrocenyl-n-nonyl group,ferrocenyl-n-decyl group,

cobaltcenylmethyl group, cobaltcenylethyl group,

nickelocenylmethyl group, nickelocenylethyl group;

dichlorotitanocenylmethyl group, trichlorotitaniumcyclopentadienylmethylgroup, bis(trifluomethanesulfonato)titanocenemethyl group,dichlorozirconocenylmethyl group, dimethylzirconocenylmethyl group,diethoxyzirconocenylmethyl group, bis(cyclopentadienyl)chromiummethylgroup, bis(cyclopentadienyl)dichloromolybdenummethyl group,bis(cyclopentadienyl)dichlorohafniummethyl group,bis(cyclopentadienyl)dichloroniobiummethyl group,bis(cyclopentadienyl)rutheniummethyl group,bis(cyclopentadienyl)vanadiummethyl group andbis(cyclopentadienyl)dichlorovanadiummethyl group;

metallocenylalkyloxy-substituted alkyl groups of 12 to 30 in carbonnumber, such as ferrocenylmethoxymethyl group, ferrocenylmethoxyethylgroup, ferrocenylmethoxypropyl group, ferrocenylmethoxybutyl group,ferrocenylmethoxypentyl group, ferrocenylmethoxyhexyl group,ferrocenylmethoxyheptyl group, ferrocenylmethoxyoctyl group,ferrocenylmethoxynonyl group, ferrocenylmethoxydecyl group,ferrocenylethoxymethyl group, ferrocenylethoxyethyl group,ferrocenylethoxypropyl group, ferrocenylethoxybutyl group,ferrocenylethoxypentyl group, ferrocenylethoxyhexyl group,ferrocenylethoxyheptyl group, ferrocenylethoxyoctyl group,ferrocenylethoxynonyl group, ferrocenylethoxydecyl group;

cobaltcenylmethoxymethyl group, cobaltcenylmethoxyethyl group;

nickelocenylmethoxymethyl group, nickelocenylmethoxyethyl group;

dichlorotitanocenylmethoxymethyl group,trichlorotitaniumcyclopentadienylmethoxyethyl group,bis(trifluoromethanesulfonato)titanocenemethoxypropyl group,dichlorozirconocenylmethoxybutyl group,dimethylzirconocenylmethoxypentyl group,diethoxyzirconocenylmethoxymethyl group,bis(cyclopentadienyl)chromiummethoxyhexyl group,bis(cyclopentadienyl)dichlorohafniummethoxymethyl group,bis(cyclopentadienyl)dichloroniobiummethoxyoctyl group,bis(cyclopentadienyl)rutheniummethoxymethyl group,bis(cyclopentadienyl)vanadiummethoxymethyl group,bis(cyclopentadienyl)dichlorovanadiummethoxyethyl group andosmocenylmethoxyethyl group;

metallocenylcarbonyloxy-substituted alkyl groups of 12 to 30 in carbonnumber, such as ferrocenecarbonyloxymethyl group,ferrocenecarbonyloxyethyl group, ferrocenecarbonyloxypropyl group,ferrocenecarbonyloxybutyl group, ferrocenecarbonyloxypentyl group,ferrocenecarbonyloxyhexyl group, ferrocenecarbonyloxyheptyl group,ferrocenecarbonyloxyoctyl group, ferrocenecarbonyloxynonyl group,ferrocenecarbonyloxydecyl group;

cobaltcenecarbonyloxymethyl group, cobaltcenecarbonyloxyethyl group,

nickelocenecarbonyloxymethyl group, nickelocenecarbonyloxyethyl group,

dichlorotitanocenylcarbonyloxymethyl group,trichlorotitaniumcyclopentadienylcarbonyloxyethyl group,bis(trifluoromethanesulfonato)titanocenecarbonyloxymethoxyp ropyl group,dichlorozirconocenecarbonyloxybutyl group,dimethylzirconocenecarbonyloxypentyl group,diethoxyzirconocenecarbonyloxymethyl group,bis(cyclopentadienyl)chromiumcarbonyloxyhexyl group,bis(cyclopentadienyl)dichlorohafniumcarbonyloxymethyl group,bis(cyclopentadienyl)dichloroniobiumcarbonyloxyoctyl group,bis(cyclopentadienyl)rutheniumcarbonyloxymethyl group,bis(cyclopentadienyl)vanadiumcarbonyloxymethyl group,bis(cyclopentadienyl)dichlorovanadiumcarbonyloxyethyl group andbis(cyclopentadienyl)osmiumcarbonyloxyethyl group;

and the like.

Examples of the substituted or unsubstituted aralkyl groups used for R¹to R¹⁶ are aralkyl groups which may have the substituents similar to theabove-mentioned alkyl groups, and are preferably aralkyl groups of 7 to15 in carbon number and the like, such as benzyl group, nitrobenzylgroup, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group,dimethylbenzyl group, trimethylbenzyl group, trifluoromethylbenzylgroup, naphthylmethyl group, nitronaphthylmethyl group,cyanonaphthylmethyl group, hydroxynaphthylmethyl group,methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group andfluorene-9-ylethyl group.

Examples of the substituted or unsubstituted aryl groups used for R¹ toR¹⁶ are aryl groups which may have the substituents similar to theabove-mentioned alkyl groups, and are preferably aryl groups of 6 to 15in carbon number and the like, such as phenyl group, nitrophenyl group,cyanophenyl group, hydroxyphenyl group, methylphenyl group, ethylphenylgroup, xylyl group, mesityl group, trifluoromethylphenyl group, naphthylgroup, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group,methylnaphthyl group, trifluoromethylnaphthyl group,methoxycarbonylphenyl group, 4-(5′-methylbenzoxazole-2′-yl)phenyl groupand dibutylaminocarbonylphenyl group.

Also, regarding aryl groups having oxygen atoms, substituted orunsubstituted sulfur atoms, and substituted or unsubstituted nitrogenatoms between carbon atoms, that is, heteroaryl groups; specificexamples of the substituted or unsubstituted heteroaryl groups used forR¹ to R¹⁶ are heteroaryl groups which may have the substituents similarto the aforementioned alkyl groups, and are preferably: unsubstitutedheteroaryl groups such as furanyl group, pyrrolyl group, 3-pyrrolinogroup, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolylgroup, 1,2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolylgroup, 1,3,4-thiadiazolyl group, pyridinyl group, pyridazinyl group,pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group,benzofuranyl group, indolyl group, thionaphcenyl group, benzimidazolylgroup, benzothiazolyl group, benzotriazol-2-yl group, benzotriazol-1-ylgroup, prinyl group, quinolinyl group, isoquinolinyl group, coumarinylgroup, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group,carbazolyl group, phenanthronilyl group, phenothiazinyl group, flavonylgroup, phthalimidyl group and naphthylimidyl group;

or heteroaryl groups substituted by the following substituents: that is

halogen atoms such as fluorine atom, chlorine atom, bromine atom andiodine atom;

cyano group;

alkyl groups such as methyl group, ethyl group, propyl group, butylgroup, pentyl group, hexyl group, heptyl group, octyl group, decylgroup, methoxymethyl group, ethoxyethyl group, ethoxymethyl group andtrifluoromethyl group; aralkyl groups such as benzyl group and phenethylgroup; aryl groups such as phenyl group, tolyl group, naphthyl group,xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group;

alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxygroup, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group,nonyloxy group, decyloxy group, 2-ethylhexyloxy group,3,5,5-trimethylhexyloxy group, ferrocenemethoxy group, cobaltcenemethoxygroup and nickelocenemethoxy group;

aralkyloxy groups such as benzyloxy group and phenethyloxy group;

aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group,xylyloxy group, mesityloxy group, chlorophenoxy group and methoxyphenoxygroup; alkenyl groups such as vinyl group, allyl group, butenyl group,butadienyl group, pentenyl group, cyclopentadienyl group and octenylgroup;

alkenyloxy groups such as vinyloxy group, allyloxy group, butenyloxygroup, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy groupand octenyloxy group;

alkylthio groups such as methylthio group, ethylthio group, propylthiogroup, butylthio group, pentylthio group, hexylthio group, heptylthiogroup, octylthio group, decylthio group, methoxymethylthio group,ethoxyethylthio group, ethoxyethylthio group and trifluoromethylthiogroup;

aralkylthio groups such as benzylthio group and phenethylthio group;

arylthio groups such as phenylthio group, tolylthio group, naphthylthiogroup, xylylthio group, mesylthio group, chlorophenylthio group andmethoxyphenylthio group;

dialkylamino groups such as dimethylamino group, diethylamino group,dipropylamino group and dibutylamino group;

acyl groups such as acetyl group, propionyl group, butanoyl group,ferrocenecarbonyl group, cobaltcenecarbonyl group andnickelocenecarbonyl group;

alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonylgroup, ferrocenemethoxycarbonyl group,1-methylferrocene-1′-ylmethoxycarbonyl group, cobaltcenylmethoxycarbonylgroup and nickelocenylmethoxycarbonyl group;

aralkyloxycarbonyl groups such as benzyloxycarbonyl group andphenethyloxycarbonyl group;

aryloxycarbonyl groups such as phenoxycarbonyl group, tolyloxycarbonylgroup, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonylgroup, chlorophenoxycarbonyl group and methoxyphenoxycarbonyl group;

alkenyloxycarbonyl groups such as vinyloxycarbonyl group,allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonylgroup, cyclopentadienyloxy group, pentenyloxycarbonyl group andoctenyloxycarbonyl group;

alkylaminocarbonyl groups, specifically monoalkylaminocarbonyl groups of2 to 10 in carbon number, such as methylaminocarbonyl group,ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonylgroup, pentylaminocarbonyl group, hexylaminocarbonyl group,heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonylgroup, 3,5,5-trimethylhexylaminocarbonyl group and2-ethylhexylaminocarbonyl group, dialkylaminocarbonyl groups of 3 to 20in carbon number, such as dimethylaminocarbonyl group,diethylaminocarbonyl group, dipropylaminocarbonyl group,dibutylaminocarbonyl group, dipentylaminocarbonyl group,dihexylaminocarbonyl group, diheptylaminocarbonyl group,dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonylgroup, 4-methylpiperazinocarbonyl group and 4-ethylpiperazinocarbonylgroup;

heterocyclic groups such as furanyl group, pyrrolyl group, 3-pyrrolinogroup, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group,2-pyrazolinyl group, pyrazolidinyl group, imidazolyl group, oxazolylgroup, thiazolyl group, 1,2,3-oxadiazolyl group, 1,2,3-triazolyl group,1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group,pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group,pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinylgroup, triazinyl group, benzofuranyl group, indolyl group, thionaphcenylgroup, benzimidazolyl group, benzothiazolyl group, prinyl group,quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinylgroup, quinoxalinyl group, dibenzofuranyl group, carbazolyl group,phenanthronilyl group, phenothiazinyl group and flavonyl group;

metallocenyl groups such as ferrocenyl group, cobaltcenyl group,nickelocenyl group, ruthenocenyl group, osmocenyl group and titanocenylgroup; and the like.

Examples of the substituted or unsubstituted alkenyl groups used for R¹to R¹⁶ are alkenyl groups which may have the substituents similar to theabove-mentioned alkyl groups, and are preferably alkenyl groups of 2 to10 in carbon number, such as vinyl group, propenyl group, 1-butenylgroup, iso-butenyl group, 1-pentenyl group, 2-pentenyl group,2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenylgroup, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group,2-cyano-2-methylsulfonvinyl group, styryl group and 4-phenyl-2-butenylgroup.

Also, as the substituted hydrocarbon radicals shown by R¹ to R¹⁶,hydrocarbon radicals whose carbon atoms directly linked to azaannulenerings are substituted by oxo groups can be mentioned. As specificexamples, substituted or unsubstituted acyl groups; carboxyl groups;substituted or unsubstituted hydrocarbonoxycarbonyl groups such asalkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl groupand alkenyloxycarbonyl group; aminocarbonyl groups; and substituted orunsubstituted hydrocarbonaminocarbonyl groups such as monosubstitutedaminocarbonyl group and disubstituted aminocarbonyl group can bementioned.

Examples of the substituted or unsubstituted acyl groups used for R¹ toR¹⁶ are acyl groups which may have the substituents similar to theabove-mentioned alkyl groups, and are preferably acyl groups of 1 to 15in carbon number, such as formyl group, methylcarbonyl group,ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group,n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group,t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group,neopentylcarbonyl group, 2-methylbutylcarbonyl group, benzoyl group,methylbenzoyl group, ethylbenzoyl group, tolylcarbonyl group,propylbenzoyl group, 4-t-butylbenzoyl group, nitrobenzylcarbonyl group,3-butoxy-2-naphthoyl group, cinnamoyl group, ferrocenecarbonyl group and1-methylferrocene-1′-carbonyl group.

Examples of the substituted or unsubstituted alkoxycarbonyl groups usedfor R¹ to R¹⁶ are alkoxycarbonyl groups which may have the substituentssimilar to the above-mentioned alkyl groups, and are preferably:alkoxycarbonyl groups of 2 to 11 in carbon number, such asmethoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group,iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonylgroup, sec-butoxycarbonyl group, t-butoxycarbonyl group,n-pentoxycarbonyl group, iso-pentoxycarbonyl group, neopentoxycarbonylgroup, 2-pentoxycarbonyl group, 2-ethylhexyloxycarbonyl group,3,5,5-trimethylhexyloxycarbonyl group, decalyloxycarbonyl group,cyclohexyloxycarbonyl group, chloroethoxycarbonyl group,hydroxymethoxycarbonyl group and hydroxyethoxycarbonyl group;

alkoxy-substituted alkoxycarbonyl groups of 3 to 11 in carbon number,such as methoxymethoxycarbonyl group, methoxyethoxycarbonyl group,ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group,butoxyethoxycarbonyl group, pentoxyethoxycarbonyl group,hexyloxyethoxycarbonyl group, butoxybutoxycarbonyl group,hexyloxybutoxycarbonyl group, hydroxymethoxymethoxycarbonyl group andhydroxyethoxyethoxycarbonyl group;

alkoxyalkoxy-substituted alkoxycarbonyl groups of 4 to 11 in carbonnumber, such as methoxymethoxymethoxycarbonyl group,methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group,propoxyethoxyethoxycarbonyl group, butoxyethoxyethoxycarbonyl group,pentoxyethoxyethoxycarbonyl group and hexyloxyethoxyethoxycarbonylgroup;

metallocenyl-substituted alkoxycarbonyl groups of 11 to 20 in carbonnumber, such as ferrocenylmethoxycarbonyl group,ferrocenylethoxycarbonyl group, ferrocenylpropoxycarbonyl group,ferrocenylbutoxycarbonyl group, ferrocenylpentyloxycarbonyl group,ferrocenylhexyloxycarbonyl group, ferrocenylheptyloxycarbonyl group,ferrocenyloctyloxycarbonyl group, ferrocenylnonyloxycarbonyl group,ferrocenyldecyloxycarbonyl group, cobaltcenylmethoxycarbonyl group,cobaltcenylethoxycarbonyl group, nickelocenylmethoxycarbonyl group,nickelocenylethoxycarbonyl group, dichlorotitanocenylmethoxycarbonylgroup, trichlorotitaniumcyclopentadienylmethoxycarbonyl group,bis(trifluoromethanesulfonato)titanocenemethoxycarbonyl group,dichlorozirconocenylmethoxycarbonyl group,dimethylzirconocenylmethoxycarbonyl group,diethoxyzirconocenylmethoxycarbonyl group,bis(cyclopentadienyl)chromiummethoxycarbonyl group,bis(cyclopentadienyl)dichlorohafniummethoxycarbonyl group,bis(cyclopentadienyl)dichloroniobiummethoxycarbonyl group,bis(cyclopentadienyl)rutheniummethoxycarbonyl group,bis(cyclopentadienyl)vanadiummethoxycarbonyl group,bis(cyclopentadienyl)dichlorovanadiummethoxycarbonyl group andbis(cyclopentadienyl)osmiummethoxycarbonyl group;

and the like.

Examples of the substituted or unsubstituted aralkyloxycarbonyl groupsused for R¹ to R¹⁶ are aralkyloxycarbonyl groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably aralkyloxycarbonyl groups of 8 to 16 in carbon number and thelike, such as benzyloxycarbonyl group, nitrobenzyloxycarbonyl group,cyanobenzyloxycarbonyl group, hydroxybenzyloxycarbonyl group,methylbenzyloxycarbonyl group, trifluoromethylbenzyloxycarbonyl group,naphthylmethoxycarbonyl group, nitronaphthylmethoxycarbonyl group,cyanonaphthylmethoxycarbonyl group, hydroxynaphthylmethoxycarbonylgroup, methylnaphthylmethoxycarbonyl group,trifluoromethylnaphthylmethoxycarbonyl group andfluorene-9-ylethoxycarbonyl group.

Examples of the substituted or unsubstituted aryloxycarbonyl groups usedfor R¹ to R¹⁶ are aryloxycarbonyl groups which may have the substituentssimilar to the above-mentioned aryl groups, and are preferablyaryloxycarbonyl groups of 7 to 11 in carbon number, such asphenoxycarbonyl group, 2-methylphenoxycarbonyl group,4-methylphenoxycarbonyl group, 4-t-butylphenoxycarbonyl group,2-methoxyphenoxycarbonyl group, 4-iso-propylphenoxycarbonyl group,naphthoxycarbonyl group, ferrocenyloxycarbonyl group,cobaltcenyloxycarbonyl group, nickelocenyloxycarbonyl group,zirconocenyloxycarbonyl group, octamethylferrocenyloxycarbonyl group,octamethylcobaltcenyloxycarbonyl group,octamethylnickelocenyloxycarbonyl group andoctamethylzirconocenyloxycarbonyl group.

Examples of the substituted or unsubstituted alkenyloxycarbonyl groupsused for R¹ to R¹⁶ are alkenyloxycarbonyl groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably alkenyloxycarbonyl groups of 3 to 11 in carbon number, suchas vinyloxycarbonyl group, propenyloxycarbonyl group,1-butenyloxycarbonyl group, iso-butenyloxycarbonyl group,1-pentenyloxycarbonyl group, 2-pentenyloxycarbonyl group,cyclopentadienyloxycarbonyl group, 2-methyl-1-butenyloxycarbonyl group,3-methyl-1-butenyloxycarbonyl group, 2-methyl-2-butenyloxycarbonylgroup, 2,2-dicyanovinyloxycarbonyl group,2-cyano-2-methylcarboxylvinyloxycarbonyl group,2-cyano-2-methylsulfonvinyloxycarbonyl group, styryloxycarbonyl groupand 4-phenyl-2-butenyloxycarbonyl group.

Examples of the monosubstituted aminocarbonyl groups used for R¹ to R¹⁶are monosubstituted aminocarbonyl groups which may have the substituentssimilar to the above-mentioned alkyl groups, and are preferably:monoalkylaminocarbonyl groups of 2 to 11 in carbon number, such asmethylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonylgroup, butylaminocarbonyl group, pentylaminocarbonyl group,hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonylgroup, (2-ethylhexyl)aminocarbonyl group, cyclohexylaminocarbonyl group,(3,5,5-trimethylhexyl)aminocarbonyl group, nonylaminocarbonyl group anddecylaminocarbonyl group;

monoaralkylaminocarbonyl groups of 8 to 11 in carbon number, such asbenzylaminocarbonyl group, phenethylaminocarbonyl group,(3-phenylpropylaminocarbonyl group, (4-ethylbenzyl)aminocarbonyl group,(4-isopropylbenzyl)aminocarbonyl group, (4-methylbenzyl)aminocarbonylgroup, (4-ethylbenzyl)aminocarbonyl group, (4-allylbenzyl)aminocarbonylgroup, [4-(2-cyanoethyl)benzyl]aminocarbonyl group and[4-(2-acetoxyethyl)benzyl]aminocarbonyl group;

monoarylaminocarbonyl groups of 7 to 11 in carbon number, such asanilinocarbonyl group, naphthylaminocarbonyl group, toluidinocarbonylgroup, xylidinocarbonyl group, ethylanilinocarbonyl group,isopropylanilinocarbonyl group, methoxyanilinocarbonyl group,ethoxyanilinocarbonyl group, chloroanilinocarbonyl group,acetylanilinocarbonyl group, methoxycarbonylanilinocarbonyl group,ethoxycarbonylanilinocarbonyl group, propoxycarbonylanilinocarbonylgroup, 4-methylanilinocarbonyl group and 4-ethylanilinocarbonyl group;

monoalkenylaminocarbonyl groups of 3 to 11 in carbon number, such asvinylaminocarbonyl group, allylaminocarbonyl group, butenylaminocarbonylgroup, pentenylaminocarbonyl group, hexenylaminocarbonyl group,cyclohexenylaminocarbonyl group, octadienylaminocarbonyl group andadamantenylaminocarbonyl group; and the like.

Examples of the disubstituted aminocarbonyl groups used for R¹ to R¹⁶are disubstituted aminocarbonyl groups which may have the substituentssimilar to the above-mentioned alkyl groups, and are preferably:dialkylaminocarbonyl groups of 3 to 17 in carbon number, such asdimethylaminocarbonyl group, diethylaminocarbonyl group,methylethylaminocarbonyl group, dipropylaminocarbonyl group,dibutylaminocarbonyl group, di-n-hexylaminocarbonyl group,dicyclohexylaminocarbonyl group, dioctylaminocarbonyl group,pyrrolidinocarbonyl group, piperidinocarbonyl group, morpholinocarbonylgroup, bis(methoxyethyl)aminocarbonyl group,bis(ethoxyethyl)aminocarbonyl group, bis(propoxyethyl)aminocarbonylgroup, bis(butoxyethyl)aminocarbonyl group,di(acetyloxyethyl)aminocarbonyl group, di(hydroxyethyl)aminocarbonylgroup, N-ethyl-N-(2-cyanoethyl)aminocarbonyl group anddi(propionyloxyethyl)aminocarbonyl group;

diaralkylaminocarbonyl groups of 15 to 21 in carbon number, such asdibenzylaminocarbonyl group, diphenethylaminocarbonyl group,bis(4-ethylbenzyl)aminocarbonyl group andbis(4-isopropylbenzyl)aminocarbonyl group;

diarylaminocarbonyl groups of 13 to 15 in carbon number, such asdiphenylaminocarbonyl group, ditolylaminocarbonyl group andN-phenyl-N-tolylaminocarbonyl group;

dialkenylaminocarbonyl groups of 5 to 13 in carbon number, such asdivinylaminocarbonyl group, diallylaminocarbonyl group,dibutenylaminocarbonyl group, dipentenylaminocarbonyl group,dihexenylaminocarbonyl group and N-vinyl-N-allylaminocarbonyl group;

and disubstituted aminocarbonyl groups of 4 to 11 in carbon numbercontaining substituents selected from substituted or unsubstituted alkylgroups, aralkyl groups, aryl groups and alkenyl groups, such asN-phenyl-N-allylaminocarbonyl group,N-(2-acetyloxyethyl)-N-ethylaminocarbonyl group,N-tolyl-N-methylaminocarbonyl group, N-vinyl-N-methylaminocarbonyl groupand N-benzyl-N-allylaminocarbonyl group.

As specific examples of the substituted or unsubstituted hydroxy groupsshown by R¹ to R¹⁶, hydroxyl groups; and substituted or unsubstitutedhydrocarbonoxy groups such as alkoxy group, aralkyloxy group, aryloxygroup and alkenyloxy group, which may have oxygen atoms, sulfur atoms,and substituted or unsubstituted nitrogen atoms between carbon atoms,can be mentioned.

Examples of the substituted or unsubstituted alkoxy groups used for R¹to R¹⁶ are: normal chain, branched-chain or cyclic unsubstituted alkoxygroups of 1 to 15 in carbon number, such as methoxy group, ethoxy group,n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group,tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxygroup, tert-pentyloxy group, sec-pentyloxy group, cyclopentyloxy group,n-hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group,3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxygroup, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group,2,3-dimethylbutoxy group, 1,1,2-trimethylpropoxy group,1,2,2-trimethylpropoxy group, ethylbutoxy group, 1-ethyl-2-methylpropoxygroup, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxygroup, methylhexyloxy group, dimethylpentyloxy group, ethylpentyloxygroup, trimethylbutoxy group, 1-ethyl-1-methylbutoxy group,1-ethyl-2-methylbutoxy group, 1-ethyl-3-methylbutoxy group,2-ethyl-1-methylbutoxy group, 2-ethyl-3-methylbutoxy group,1-n-propylbutoxy group, 1-isopropylbutoxy group,1-isopropyl-2-methylpropoxy group, methylcyclohexyloxy group, n-octyloxygroup, 1-methylheptyloxy group, 2-methylheptyloxy group,3-methylheptyloxy group, 4-methylheptyloxy group, 5-methylheptyloxygroup, 6-methylheptyloxy group, dimethylhexyloxy group, 1-ethylhexyloxygroup, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 4-ethylhexyloxygroup, 1-n-propylpentyloxy group, 2-n-propylpentyloxy group,1-isopropylpentyloxy group, 2-isopropylpentyloxy group,1-ethyl-1-methylpentyloxy group, 1-ethyl-2-methylpentyloxy group,1-ethyl-3-methylpentyloxy group, 1-ethyl-4-methylpentyloxy group,2-ethyl-1-methylpentyloxy group, 2-ethyl-2-methylpentyloxy group,2-ethyl-3-methylpentyloxy group, 2-ethyl-4-methylpentyloxy group,3-ethyl-1-methylpentyloxy group, 3-ethyl-2-methylpentyloxy group,3-ethyl-3-methylpentyloxy group, 3-ethyl-4-methylpentyloxy group,trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group,1-sec-butylbutoxy group, 1-tert-butylbutoxy group, 2-tert-butylbutoxygroup, 1-n-propyl-1-methylbutoxy group, 1-n-propyl-2-methylbutoxy group,1-n-propyl-3-methylbutoxy group, 1-isopropyl-1-methylbutoxy group,1-isopropyl-2-methylbutoxy group, 1-isopropyl-3-methylbutoxy group,1,1-diethylbutoxy group, 1,2-diethylbutoxy group,1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group,1-ethyl-2,3-dimethylbutoxy group, 2-ethyl-1,1-dimethylbutoxy group,2-ethyl-1,2-dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group,2-ethyl-2,3-dimethylbutoxy group, 1,1,3,3-tetramethylbutoxy group,1,2-dimethylcyclohexyloxy group, 1,3-dimethylcyclohexyloxy group,1,4-dimethylcyclohexyloxy group, ethylcyclohexyloxy group, n-nonyloxygroup, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxygroup, n-dodecyloxy group, 1-adamantyloxy group and n-pentadecyloxygroup;

alkoxy-substituted alkoxy groups of 2 to 15 in carbon number, such asmethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group,n-propoxyethoxy group, isopropoxyethoxy group, n-butoxyethoxy group,isobutoxyethoxy group, tert-butoxyethoxy group, sec-butoxyethoxy group,n-pentyloxyethoxy group, isopentyloxyethoxy group, tert-pentyloxyethoxygroup, sec-pentyloxyethoxy group, cyclopentyloxyethoxy group,n-hexyloxyethoxy group, ethylcyclohexyloxyethoxy group, n-nonyloxyethoxygroup, (3,5,5-trimethylhexyloxy)ethoxy group,(3,5,5-trimethylhexyloxy)butoxy group, n-decyloxyethoxy group,n-undecyloxyethoxy group, n-dodecyloxyethoxy group, 3-methoxypropoxygroup, 3-ethoxypropoxy group, 3-(n-propoxy)propoxy group,2-isopropoxypropoxy group, 2-methoxybutoxy group, 2-ethoxybutoxy group,2-(n-propoxy)butoxy group, 4-isopropoxybutoxy group, decalyloxyethoxygroup and adamantyloxyethoxy group;

alkoxyalkoxy-substituted normal chain, branched-chain or cyclic alkoxygroups of 3 to 15 in carbon number, such as methoxymethoxymethoxy group,ethoxymethoxymethoxy group, propoxymethoxymethoxy group,butoxymethoxymethoxy group, methoxyethoxymethoxy group,ethoxyethoxymethoxy group, propoxyethoxymethoxy group,butoxyethoxymethoxy group, methoxypropoxymethoxy group,ethoxypropoxymethoxy group, propoxypropoxymethoxy group,butoxypropoxymethoxy group, methoxybutoxymethoxy group,ethoxybutoxymethoxy group, propoxybutoxymethoxy group,butoxybutoxymethoxy group, methoxymethoxyethoxy group,ethoxymethoxyethoxy group, propoxymethoxyethoxy group,butoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxygroup, propoxyethoxyethoxy group, butoxyethoxyethoxy group,methoxypropoxyethoxy group, ethoxypropoxyethoxy group,propoxypropoxyethoxy group, butoxypropoxyethoxy group,methoxybutoxyethoxy group, ethoxybutoxyethoxy group, propoxybutoxyethoxygroup, butoxybutoxyethoxy group, methoxymethoxypropoxy group,ethoxymethoxypropoxy group, propoxymethoxypropoxy group,butoxymethoxypropoxy group, methoxyethoxypropoxy group,ethoxyethoxypropoxy group, propoxyethoxypropoxy group,butoxyethoxypropoxy group, methoxypropoxypropoxy group,ethoxypropoxypropoxy group, propoxypropoxypropoxy group,butoxypropoxypropoxy group, methoxybutoxypropoxy group,ethoxybutoxypropoxy group, propoxybutoxypropoxy group,butoxybutoxypropoxy group, methoxymethoxybutoxy group,ethoxymethoxybutoxy group, propoxymethoxybutoxy group,butoxymethoxybutoxy group, methoxyethoxybutoxy group, ethoxyethoxybutoxygroup, propoxyethoxybutoxy group, butoxyethoxybutoxy group,methoxypropoxybutoxy group, ethoxypropoxybutoxy group,propoxypropoxybutoxy group, butoxypropoxybutoxy group,methoxybutoxybutoxy group, ethoxybutoxybutoxy group, propoxybutoxybutoxygroup, butoxybutoxybutoxy group, (4-ethylcyclohexyloxy)ethoxyethoxygroup, (2-ethyl-1-hexyloxy)ethoxypropoxy group and[4-(3,5,5-trimethylhexyloxy)butoxy]ethoxy group;

alkoxycarbonyl-substituted alkoxy groups of 3 to 10 in carbon number,such as methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group,n-propoxycarbonylmethoxy group, isopropoxycarbonylmethoxy group and(4′-ethylcyclohexyloxy)carbonylmethoxy group;

acyl-substituted alkoxy groups of 3 to 10 in carbon number, such asacetylmethoxy group, ethylcarbonylmethoxy group, octylcarbonylmethoxygroup and phenacyloxy group;

acyloxy-substituted alkoxy groups of 3 to 10 in carbon number, such asacetyloxymethoxy group, acetyloxyethoxy group, acetyloxyhexyloxy groupand butanoyloxycyclohexyloxy group;

alkylamino-substituted alkoxy groups of 2 to 10 in carbon number, suchas methylaminomethoxy group, 2-methylaminoethoxy group,2-(2-methylaminoethoxy)ethoxy group, 4-methylaminobutoxy group,1-methylaminopropane-2-yloxy group, 3-methylaminopropoxy group,2-methylamino-2-methylpropoxy group, 2-ethylaminoethoxy group,2-(2-ethylaminoethoxy)ethoxy group, 3-ethylaminopropoxy group,1-ethylaminopropoxy group, 2-isopropylaminoethoxy group,2-(n-butylamino)ethoxy group, 3-(n-hexylamino)propoxy group and4-(cyclohexylamino)butyloxy group;

alkylaminoalkoxy-substituted alkoxy groups of 3 to 10 in carbon number,such as methylaminomethoxymethoxy group, methylaminoethoxyethoxy group,methylaminoethoxypropoxy group, ethylaminoethoxypropoxy group and4-(2′-isobutylaminopropoxy)butoxy group;

dialkylamino-substituted alkoxy groups of 3 to 15 in carbon number, suchas dimethylaminomethoxy group, 2-dimethylaminoethoxy group,2-(2-dimethylaminoethoxy)ethoxy group, 4-dimethylaminobutoxy group,1-dimethylaminopropane-2-yloxy group, 3-dimethylaminopropoxy group,2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group,2-(2-diethylaminoethoxy)ethoxy group, 3-diethylaminopropoxy group,1-diethylaminopropoxy group, 2-diisopropylaminoethoxy group,2-(di-n-butylamino)ethoxy group, 2-piperidylethoxy group and3-(di-n-hexylamino)propoxy group;

dialkylaminoalkoxy-substituted alkoxy groups of 4 to 15 in carbonnumber, such as dimethylaminomethoxymethoxy group,dimethylaminoethoxyethoxy group, dimethylaminoethoxypropoxy group,diethylaminoethoxypropoxy group and 4-(2′-diisobutylaminopropoxy)butoxygroup;

alkylthio-substituted alkoxy groups of 2 to 15 in carbon number, such asmethylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxygroup, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group,2-n-butylthioethoxy group, 2-isobutylthioethoxy group and(3,5,5-trimethylhexylthio)hexyloxy group;

and the like; preferably alkoxy groups of 1 to 10 in carbon number, suchas methoxy group, ethoxy group, n-propoxy group, iso-propoxy group,n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group,n-pentoxy group, iso-pentoxy group, neopentoxy group, 2-methylbutoxygroup, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, decalyloxygroup, methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxygroup and ethoxyethoxyethoxy group.

Examples of the substituted or unsubstituted aralkyloxy groups used forR¹ to R¹⁶ are aralkyloxy groups which may have the substituents similarto the above-mentioned alkyl groups, and are preferably aralkyloxygroups of 7 to 15 in carbon number and the like, such as benzyloxygroup, nitrobenzyloxy group, cyanobenzyloxy group, hydroxybenzyloxygroup, methylbenzyloxy group, trifluoromethylbenzyloxy group,naphthylmethoxy group, nitronaphthylmethoxy group, cyanonaphthylmethoxygroup, hydroxynaphthylmethoxy group, methylnaphthylmethoxy group,trifluoromethylnaphthylmethoxy group and fluorene-9-ylethoxy group.

Examples of the substituted or unsubstituted aryloxy groups used for R¹to R¹⁶ are aryloxy groups which may have the substituents similar to theabove-mentioned alkyl groups, and are preferably aryloxy groups of 6 to18 in carbon number, such as phenylthio group, 2-methylphenylthio group,4-methylphenylthio group, 4-t-butylphenylthio group, 2-methoxyphenylthiogroup, 4-iso-propylphenylthio group, tolyloxy group, naphthoxy group,ferrocenyloxy group, cobaltcenyloxy group, nickelocenyloxy group,octamethylferrocenyloxy group, octamethylcobaltcenyloxy group andoctamethylnickelocenyloxy group.

Also, as examples of substituted or unsubstituted heteroaryloxy groupsused for R¹ to R¹⁶, which are aryloxy groups having oxygen atoms,substituted or unsubstituted sulfur atoms, and substituted orunsubstituted nitrogen atoms between carbon atoms, heteroaryloxy groupsmade by the aforementioned heteroaryl groups bonding with oxygen atomscan be mentioned.

Examples of the substituted or unsubstituted alkenyloxy groups used forR¹ to R¹⁶ are alkenyloxy groups which may have the substituents similarto the above-mentioned alkyl groups, and are preferably alkenyloxygroups of 2 to 10 in carbon number, such as vinyloxy group, propenyloxygroup, 1-butenyloxy group, iso-butenyloxy group, 1-pentenyloxy group,2-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-1-butenyloxygroup, 2-methyl-2-butenyloxy group, cyclopentadienyloxy group,2,2-dicyanovinyloxy group, 2-cyano-2-methylcarboxylvinyloxy group,2-cyano-2-methylsulfonvinyloxy group, styryloxy group,4-phenyl-2-butenyloxy group and cinnamylalkoxy group.

Also, as the substituted hydrocarbonoxy groups shown by R¹ to R¹⁶,hydrocarbonoxy groups whose carbon atoms directly linked to oxygen atomsdirectly linked to azaannulene rings are substituted by oxo groups canbe mentioned. As specific examples, substituted or unsubstituted acyloxygroups; substituted or unsubstituted hydrocarbonoxycarbonyloxy groupssuch as alkoxycarbonyloxy group, aralkyloxycarbonyloxy group,aryloxycarbonyloxy group and alkenyloxycarbonyloxy group; substituted orunsubstituted hydrocarbonaminocarbonyloxy groups such as monosubstitutedaminocarbonyloxy group and disubstituted aminocarbonyloxy group; and thelike can be mentioned.

Examples of the substituted or unsubstituted acyloxy groups used for R¹to R¹⁶ are acyloxy groups which may have the substituents similar to theabove-mentioned alkyl groups, and are preferably acyloxy groups of 1 to15 in carbon number, such as formyloxy group, methylcarbonyloxy group,ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxygroup, n-butylcarbonyloxy group, iso-butylcarbonyloxy group,sec-butylcarbonyloxy group, t-butylcarbonyloxy group,n-pentylcarbonyloxy group, iso-pentylcarbonyloxy group,neopentylcarbonyloxy group, 2-methylbutylcarbonyloxy group, benzoyloxygroup, methylbenzoyloxy group, ethylbenzoyloxy group, tolylcarbonyloxygroup, propylbenzoyloxy group, 4-t-butylbenzoyloxy group,nitrobenzylcarbonyloxy group, 3-butoxy-2-naphthoyloxy group,cinnamoyloxy group, ferrocenecarbonyloxy group and1-methylferrocene-1′-carbonyloxy group.

Examples of the substituted or unsubstituted alkoxycarbonyloxy groupsused for R¹ to R¹⁶ are alkoxycarbonyloxy groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably: alkoxycarbonyloxy groups of 2 to 11 in carbon number, suchas methoxycarbonyloxy group, ethoxycarbonyloxy group,n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group,n-butoxycarbonyloxy group, iso-butoxycarbonyloxy group,sec-butoxycarbonyloxy group, t-butoxycarbonyloxy group,n-pentoxycarbonyloxy group, iso-pentoxycarbonyloxy group,neopentoxycarbonyloxy group, 2-pentoxycarbonyloxy group,2-ethylhexyloxycarbonyloxy group, 3,5,5-trimethylhexyloxycarbonyloxygroup, decalyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group,chloroethoxycarbonyloxy group, hydroxymethoxycarbonyloxy group andhydroxyethoxycarbonyloxy group;

alkoxy-substituted alkoxycarbonyloxy groups of 3 to 11 in carbon number,such as methoxymethoxycarbonyloxy group, methoxyethoxycarbonyloxy group,ethoxyethoxycarbonyloxy group, propoxyethoxycarbonyloxy group,butoxyethoxycarbonyloxy group, pentoxyethoxycarbonyloxy group,hexyloxyethoxycarbonyloxy group, butoxybutoxycarbonyloxy group,hexyloxybutoxycarbonyloxy group, hydroxymethoxymethoxycarbonyloxy groupand hydroxyethoxyethoxycarbonyloxy group;

alkoxyalkoxy-substituted alkoxycarbonyloxy groups of 4 to 11 in carbonnumber, such as methoxymethoxymethoxycarbonyloxy group,methoxyethoxyethoxycarbonyloxy group, ethoxyethoxyethoxycarbonyloxygroup, propoxyethoxyethoxycarbonyloxy group,butoxyethoxyethoxycarbonyloxy group, pentoxyethoxyethoxycarbonyloxygroup and hexyloxyethoxyethoxycarbonyloxy group;

metallocenyl-substituted alkoxycarbonyloxy groups of 11 to 20 in carbonnumber, such as ferrocenylmethoxycarbonyloxy group,ferrocenylethoxycarbonyloxy group, ferrocenylpropoxycarbonyloxy group,ferrocenylbutoxycarbonyloxy group, ferrocenylpentyloxycarbonyloxy group,ferrocenylhexyloxycarbonyloxy group, ferrocenylheptyloxycarbonyloxygroup, ferrocenyloctyloxycarbonyloxy group,ferrocenylnonyloxycarbonyloxy group, ferrocenyldecyloxycarbonyloxygroup, cobaltcenylmethoxycarbonyloxy group, cobaltcenylethoxycarbonyloxygroup, nickelocenylmethoxycarbonyloxy group,nickelocenylethoxycarbonyloxy group,dichlorotitanocenylmethoxycarbonyloxy group,trichlorotitaniumcyclopentadienylmethoxycarbonyloxy group,bis(trifluoromethanesulfonato)titanocenemethoxycarbonyloxy group,dichlorozirconocenylmethoxycarbonyloxy group,dimethylzirconocenylmethoxycarbonyloxy group,diethoxyzirconocenylmethoxycarbonyloxy group,bis(cyclopentadienyl)chromiummethoxycarbonyloxy group,bis(cyclopentadienyl)dichlorohafniummethoxycarbonyloxy group,bis(cyclopentadienyl)dichloroniobiummethoxycarbonyloxy group,bis(cyclopentadienyl)rutheniummethoxycarbonyloxy group,bis(cyclopentadienyl)vanadiummethoxycarbonyloxy group,bis(cyclopentadienyl)dichlorovanadiummethoxycarbonyloxy group andbis(cyclopentadienyl)osmiummethoxycarbonyloxy group; and the like.

Examples of the substituted or unsubstituted aralkyloxycarbonyloxygroups used for R¹ to R¹⁶ are aralkyloxycarbonyloxy groups which mayhave the substituents similar to the above-mentioned alkyl groups, andare preferably aralkyloxycarbonyloxy groups of 8 to 16 in carbon numberand the like, such as benzyloxycarbonyloxy group,nitrobenzyloxycarbonyloxy group, cyanobenzyloxycarbonyloxy group,hydroxybenzyloxycarbonyloxy group, methylbenzyloxycarbonyloxy group,trifluoromethylbenzyloxycarbonyloxy group, naphthylmethoxycarbonyloxygroup, nitronaphthylmethoxycarbonyloxy group,cyanonaphthylmethoxycarbonyloxy group, hydroxynaphthylmethoxycarbonyloxygroup, methylnaphthylmethoxycarbonyloxy group,trifluoromethylnaphthylmethoxycarbonyloxy group andfluorene-9-ylethoxycarbonyloxy group.

Examples of the substituted or unsubstituted aryloxycarbonyloxy groupsused for R¹ to R¹⁶ are aryloxycarbonyloxy groups which may have thesubstituents similar to the above-mentioned aryl groups, and preferablyare aryloxycarbonyloxy groups of 7 to 11 in carbon number, such asphenoxycarbonyloxy group, 2-methylphenoxycarbonyloxy group,4-methylphenoxycarbonyloxy group, 4-t-butylphenoxycarbonyloxy group,2-methoxyphenoxycarbonyloxy group, 4-iso-propylphenoxycarbonyloxy group,naphthoxycarbonyloxy group, ferrocenyloxycarbonyloxy group,cobaltcenyloxycarbonyloxy group, nickelocenyloxycarbonyloxy group,zirconocenyloxycarbonyloxy group, octamethylferrocenyloxycarbonyloxygroup, octamethylcobaltcenyloxycarbonyloxy group,octamethylnickelocenyloxycarbonyloxy group andoctamethylzirconocenyloxycarbonyloxy group.

Examples of the substituted or unsubstituted alkenyloxycarbonyloxygroups used for R¹ to R¹⁶ are alkenyloxycarbonyloxy groups which mayhave the substituents similar to the above-mentioned alkyl groups, andare preferably alkenyloxycarbonyloxy groups of 3 to 11 in carbon number,such as vinyloxycarbonyloxy group, propenyloxycarbonyloxy group,1-butenyloxycarbonyloxy group, iso-butenyloxycarbonyloxy group,1-pentenyloxycarbonyloxy group, 2-pentenyloxycarbonyloxy group,cyclopentadienyloxycarbonyloxy group, 2-methyl-1-butenyloxycarbonyloxygroup, 3-methyl-1-butenyloxycarbonyloxy group,2-methyl-2-butenyloxycarbonyloxy group, 2,2-dicyanovinyloxycarbonyloxygroup, 2-cyano-2-methylcarboxylvinyloxycarbonyloxy group,2-cyano-2-methylsulfonvinyloxycarbonyloxy group, styryloxycarbonyloxygroup and 4-phenyl-2-butenyloxycarbonyloxy group.

Examples of the monosubstituted aminocarbonyloxy groups used for R¹ toR¹⁶ are monosubstituted aminocarbonyloxy groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably: monoalkylaminocarbonyloxy groups of 2 to 11 in carbonnumber, such as methylaminocarbonyloxy group, ethylaminocarbonyloxygroup, propylaminocarbonyloxy group, butylaminocarbonyloxy group,pentylaminocarbonyloxy group, hexylaminocarbonyloxy group,heptylaminocarbonyloxy group, octylaminocarbonyloxy group,(2-ethylhexyl)aminocarbonyloxy group, cyclohexylaminocarbonyloxy group,(3,5,5-trimethylhexyl)aminocarbonyloxy group, nonylaminocarbonyloxygroup and decylaminocarbonyloxy group;

monoaralkylaminocarbonyloxy groups of 8 to 11 in carbon number, such asbenzylaminocarbonyloxy group, phenethylaminocarbonyloxy group,(3-phenylpropylaminocarbonyloxy group, (4-ethylbenzyl)aminocarbonyloxygroup, (4-isopropylbenzyl)aminocarbonyloxy group,(4-methylbenzyl)aminocarbonyloxy group, (4-ethylbenzyl)aminocarbonyloxygroup, (4-allylbenzyl)aminocarbonyloxy group,[4-(2-cyanoethyl)benzyl]aminocarbonyloxy group and[4-(2-acetoxyethyl)benzyl]aminocarbonyloxy group;

monoarylaminocarbonyloxy groups of 7 to 11 in carbon number, such asanilinocarbonyloxy group, naphthylaminocarbonyloxy group,toluidinocarbonyloxy group, xylidinocarbonyloxy group,ethylanilinocarbonyloxy group, isopropylanilinocarbonyloxy group,methoxyanilinocarbonyloxy group, ethoxyanilinocarbonyloxy group,chloroanilinocarbonyloxy group, acetylanilinocarbonyloxy group,methoxycarbonylanilinocarbonyloxy group,ethoxycarbonylanilinocarbonyloxy group,propoxycarbonylanilinocarbonyloxy group, 4-methylanilinocarbonyloxygroup and 4-ethylanilinocarbonyloxy group;

monoalkenylaminocarbonyloxy groups of 3 to 11 in carbon number, such asvinylaminocarbonyloxy group, allylaminocarbonyloxy group,butenylaminocarbonyloxy group, pentenylaminocarbonyloxy group,hexenylaminocarbonyloxy group, cyclohexenylaminocarbonyloxy group,octadienylaminocarbonyloxy group and adamantenylaminocarbonyloxy group;and the like.

Examples of the disubstituted aminocarbonyloxy groups used for R¹ to R¹⁶are disubstituted aminocarbonyloxy groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably: dialkylaminocarbonyloxy groups of 3 to 17 in carbon number,such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group,methylethylaminocarbonyloxy group, dipropylaminocarbonyloxy group,dibutylaminocarbonyloxy group, di-n-hexylaminocarbonyloxy group,dicyclohexylaminocarbonyloxy group, dioctylaminocarbonyloxy group,pyrrolidinocarbonyloxy group, piperidinocarbonyloxy group,morpholinocarbonyloxy group, bis(methoxyethyl)aminocarbonyloxy group,bis(ethoxyethyl)aminocarbonyloxy group,bis(propoxyethyl)aminocarbonyloxy group,bis(butoxyethyl)aminocarbonyloxy group,di(acetyloxyethyl)aminocarbonyloxy group,di(hydroxyethyl)aminocarbonyloxy group,N-ethyl-N-(2-cyanoethyl)aminocarbonyloxy group anddi(propionyloxyethyl)aminocarbonyloxy group;

diaralkylaminocarbonyloxy groups of 15 to 21 in carbon number, such asdibenzylaminocarbonyloxy group, diphenethylaminocarbonyloxy group,bis(4-ethylbenzyl)aminocarbonyloxy group andbis(4-isopropylbenzyl)aminocarbonyloxy group;

diarylaminocarbonyloxy groups of 13 to 15 in carbon number, such asdiphenylaminocarbonyloxy group, ditolylaminocarbonyloxy group andN-phenyl-N-tolylaminocarbonyloxy group;

dialkenylaminocarbonyloxy groups of 5 to 13 in carbon number, such asdivinylaminocarbonyloxy group, diallylaminocarbonyloxy group,dibutenylaminocarbonyloxy group, dipentenylaminocarbonyloxy group,dihexenylaminocarbonyloxy group and N-vinyl-N-allylaminocarbonyloxygroup;

and disubstituted aminocarbonyloxy groups of 4 to 11 in carbon numbercontaining substituents selected from substituted or unsubstituted alkylgroups, aralkyl groups, aryl groups and alkenyl groups, such asN-phenyl-N-allylaminocarbonyloxy group,N-(2-acetyloxyethyl)-N-ethylaminocarbonyloxy group,N-tolyl-N-methylaminocarbonyloxy group, N-vinyl-N-methylaminocarbonyloxygroup and N-benzyl-N-allylaminocarbonyloxy group.

As specific examples of the substituted or unsubstituted mercapto groupsshown by R¹ to R¹⁶: unsubstituted mercapto groups; and substituted orunsubstituted hydrocarbonthio groups such as alkylthio group,aralkylthio group, arylthio group and alkenylthio group, which may haveoxygen atoms, substituted or unsubstituted sulfur atoms, and substitutedor unsubstituted nitrogen atoms between carbon atoms, can be mentioned.

Examples of the substituted or unsubstituted alkylthio groups used forR¹ to R¹⁶ are alkylthio groups which may have the substituents similarto the above-mentioned alkyl groups, and are preferably: normal chain,branched-chain or cyclic unsubstituted alkylthio groups of 1 to 15 incarbon number, such as methylthio group, ethylthio group, n-propylthiogroup, isopropylthio group, n-butylthio group, isobutylthio group,tert-butylthio group, sec-butylthio group, n-pentylthio group,isopentylthio group, tert-pentylthio group, sec-pentylthio group,cyclopentylthio group, n-hexylthio group, methylpentylthio group,dimethylbutylthio group, trimethylpropylthio group, 1-ethylbutylthiogroup, 2-ethylbutylthio group, 1-ethyl-2-methylpropylthio group,cyclohexylthio group, methylcyclopentylthio group, n-heptylthio group,methylhexylthio group, dimethylpentylthio group, ethylpentylthio group,trimethylbutylthio group, 1-ethyl-1-methylbutylthio group,1-ethyl-2-methylbutylthio group, 1-ethyl-3-methylbutylthio group,2-ethyl-1-methylbutylthio group, 2-ethyl-3-methylbutylthio group,1-n-propylbutylthio group, 1-isopropylbutylthio group,1-isopropyl-2-methylpropylthio group, methylcyclohexylthio group,n-octylthio group, 1-methylheptylthio group, 2-methylheptylthio group,3-methylheptylthio group, 4-methylheptylthio group, 5-methylheptylthiogroup, 6-methylheptylthio group, 1,1-dimethylhexylthio group,1,2-dimethylhexylthio group, 1,3-dimethylhexylthio group,1,4-dimethylhexylthio group, 1,5-dimethylhexylthio group,2,2-dimethylhexylthio group, 2,3-dimethylhexylthio group,2,4-dimethylhexylthio group, 2,5-dimethylhexylthio group,3,3-dimethylhexylthio group, 3,4-dimethylhexylthio group,3,5-dimethylhexylthio group, 4,4-dimethylhexylthio group,4,5-dimethylhexylthio group, 1-ethylhexylthio group, 2-ethylhexylthiogroup, 3-ethylhexylthio group, 4-ethylhexylthio group,1-n-propylpentylthio group, 2-n-propylpentylthio group,1-isopropylpentylthio group, 2-isopropylpentylthio group,1-ethyl-1-methylpentylthio group, 1-ethyl-2-methylpentylthio group,1-ethyl-3-methylpentylthio group, 1-ethyl-4-methylpentylthio group,2-ethyl-1-methylpentylthio group, 2-ethyl-2-methylpentylthio group,2-ethyl-3-methylpentylthio group, 2-ethyl-4-methylpentylthio group,3-ethyl-1-methylpentylthio group, 3-ethyl-2-methylpentylthio group,3-ethyl-3-methylpentylthio group, 3-ethyl-4-methylpentylthio group,trimethylpentylthio group, 1-n-butylbutylthio group, 1-isobutylbutylthiogroup, 1-sec-butylbutylthio group, 1-tert-butylbutylthio group,2-tert-butylbutylthio group, 1-n-propyl-1-methylbutylthio group,1-n-propyl-2-methylbutylthio group, 1-n-propyl-3-methylbutylthio group,1-isopropyl-1-methylbutylthio group, 1-isopropyl-2-methylbutylthiogroup, 1-isopropyl-3-methylbutylthio group, diethylbutylthio group,1-ethyl-1,2-dimethylbutylthio group, 1-ethyl-1,3-dimethylbutylthiogroup, 1-ethyl-2,3-dimethylbutylthio group,2-ethyl-1,1-dimethylbutylthio group, 2-ethyl-1,2-dimethylbutylthiogroup, 2-ethyl-1,3-dimethylbutylthio group,2-ethyl-2,3-dimethylbutylthio group, 1,1,3,3-tetramethylbutylthio group,1,2-dimethylcyclohexylthio group, 1,3-dimethylcyclohexylthio group,1,4-dimethylcyclohexylthio group, ethylcyclohexylthio group, n-nonylthiogroup, 3,5,5-trimethylhexylthio group, n-decylthio group, n-undecylthiogroup, n-dodecylthio group, 1-adamantylthio group and n-pentadecylthiogroup;

alkoxy-substituted alkylthio groups of 2 to 15 in carbon number, such asmethoxymethylthio group, methoxyethylthio group, ethoxyethylthio group,n-propoxyethylthio group, isopropoxyethylthio group, n-butoxyethylthiogroup, isobutoxyethylthio group, tert-butoxyethylthio group,sec-butoxyethylthio group, n-pentyloxyethylthio group,isopentyloxyethylthio group, tert-pentyloxyethylthio group,sec-pentyloxyethylthio group, cyclopentyloxyethylthio group,n-hexyloxyethylthio group, ethylcyclohexyloxyethylthio group,n-nonyloxyethylthio group, (3,5,5-trimethylhexyloxy)ethylthio group,(3,5,5-trimethylhexyloxy)butylthio group, n-decyloxyethylthio group,n-undecyloxyethylthio group, n-dodecyloxyethylthio group,3-methoxypropylthio group, 3-ethoxypropylthio group,3-(n-propoxy)propylthio group, 2-isopropoxypropylthio group,2-methoxybutylthio group, 2-ethoxybutylthio group,2-(n-propoxy)butylthio group, 4-isopropoxybutylthio group,decalyloxyethylthio group and adamantyloxyethylthio group;

alkoxyalkoxy-substituted normal chain, branched-chain or cyclicalkylthio groups of 3 to 15 in carbon number, such asmethoxymethoxymethylthio group, ethoxymethoxymethylthio group,propoxymethoxymethylthio group, butoxymethoxymethylthio group,methoxyethoxymethylthio group, ethoxyethoxymethylthio group,propoxyethoxymethylthio group, butoxyethoxymethylthio group,methoxypropoxymethylthio group, ethoxypropoxymethylthio group,propoxypropoxymethylthio group, butoxypropoxymethylthio group,methoxybutoxymethylthio group, ethoxybutoxymethylthio group,propoxybutoxymethylthio group, butoxybutoxymethylthio group,methoxymethoxyethylthio group, ethoxymethoxyethylthio group,propoxymethoxyethylthio group, butoxymethoxyethylthio group,methoxyethoxyethylthio group, ethoxyethoxyethylthio group,propoxyethoxyethylthio group, butoxyethoxyethylthio group,methoxypropoxyethylthio group, ethoxypropoxyethylthio group,propoxypropoxyethylthio group, butoxypropoxyethylthio group,methoxybutoxyethylthio group, ethoxybutoxyethylthio group,propoxybutoxyethylthio group, butoxybutoxyethylthio group,methoxymethoxypropylthio group, ethoxymethoxypropylthio group,propoxymethoxypropylthio group, butoxymethoxypropylthio group,methoxyethoxypropylthio group, ethoxyethoxypropylthio group,propoxyethoxypropylthio group, butoxyethoxypropylthio group,methoxypropoxypropylthio group, ethoxypropoxypropylthio group,propoxypropoxypropylthio group, butoxypropoxypropylthio group,methoxybutoxypropylthio group, ethoxybutoxypropylthio group,propoxybutoxypropylthio group, butoxybutoxypropylthio group,methoxymethoxybutylthio group, ethoxymethoxybutylthio group,propoxymethoxybutylthio group, butoxymethoxybutylthio group,methoxyethoxybutylthio group, ethoxyethoxybutylthio group,propoxyethoxybutylthio group, butoxyethoxybutoxy group,methoxypropoxybutylthio group, ethoxypropoxybutylthio group,propoxypropoxybutylthio group, butoxypropoxybutylthio group,methoxybutoxybutylthio group, ethoxybutoxybutylthio group,propoxybutoxybutylthio group, butoxybutoxybutylthio group,(4-ethylcyclohexyloxy)ethoxyethylthio group,(2-ethyl-1-hexyloxy)ethoxypropylthio group and[4-(3,5,5-trimethylhexyloxy)butoxy]ethylthio group;

alkoxycarbonyl-substituted alkylthio groups of 3 to 10 in carbon number,such as methoxycarbonylmethylthio group, ethoxycarbonylmethylthio group,n-propoxycarbonylmethylthio group, isopropoxycarbonylmethylthio groupand (4′-ethylcyclohexyloxy)carbonylmethylthio group;

acyl-substituted alkylthio groups of 3 to 10 in carbon number, such asacetylmethylthio group, ethylcarbonylmethylthio group,octylcarbonylmethylthio group and phenacylthio group;

acylthio-substituted alkylthio groups of 3 to 10 in carbon number, suchas acetyloxymethylthio group, acetyloxyethylthio group,acetyloxyhexylthio group and butanoyloxycyclohexylthio group;

alkylamino-substituted alkylthio groups of 2 to 10 in carbon number,such as methylaminomethylthio group, 2-methylaminoethylthio group,2-(2-methylaminoethoxy)ethylthio group, 4-methylaminobutylthio group,1-methylaminopropane-2-ylthio group, 3-methylaminopropylthio group,2-methylamino-2-methylpropylthio group, 2-ethylaminoethylthio group,2-(2-ethylaminoethoxy)ethylthio group, 3-ethylaminopropylthio group,1-ethylaminopropylthio group, 2-isopropylaminoethylthio group,2-(n-butylamino)ethylthio group, 3-(n-hexylamino)propylthio group and4-(cyclohexylamino)butylthio group;

alkylaminoalkylthio-substituted alkylthio groups of 3 to 10 in carbonnumber, such as methylaminomethoxymethylthio group,methylaminoethoxyethylthio group, methylaminoethoxypropylthio group,ethylaminoethoxypropylthio group and4-(2′-isobutylaminopropoxy)butylthio group;

dialkylamino-substituted alkylthio groups of 3 to 15 in carbon number,such as dimethylaminomethylthio group, 2-dimethylaminoethylthio group,2-(2-dimethylaminoethoxy)ethylthio group, 4-dimethylaminobutylthiogroup, 1-dimethylaminopropane-2-ylthio group, 3-dimethylaminopropylthiogroup, 2-dimethylamino-2-methylpropylthio group, 2-diethylaminoethylthiogroup, 2-(2-diethylaminoethoxy)ethylthio group, 3-diethylaminopropylthiogroup, 1-diethylaminopropylthio group, 2-diisopropylaminoethylthiogroup, 2-(di-n-butylamino)ethylthio group, 2-piperidylethylthio groupand 3-(di-n-hexylamino)propylthio group;

dialkylaminoalkylthio-substituted alkylthio groups of 4 to 15 in carbonnumber, such as dimethylaminomethoxymethylthio group,dimethylaminoethoxyethylthio group, dimethylaminoethoxypropylthio group,diethylaminoethoxypropylthio group and4-(2′-diisobutylaminopropoxy)butylthio group;

alkylthio-substituted alkylthio groups of 2 to 15 in carbon number, suchas methylthiomethylthio group, 2-methylthioethylthio group,2-ethylthioethylthio group, 2-n-propylthioethylthio group,2-isopropylthioethylthio group, 2-n-butylthioethylthio group,2-isobutylthioethylthio group and (3,5,5-trimethylhexylthio)hexylthiogroup;

and the like; more preferably alkylthio groups of 1 to 10 in carbonnumber, such as methylthio group, ethylthio group, n-propylthio group,iso-propylthio group, n-butylthio group, iso-butylthio group,sec-butylthio group, t-butylthio group, n-pentylthio group,iso-pentylthio group, neopentylthio group, 2-methylbutylthio group,n-hexylthio group, n-heptylthio group, n-octylthio group,2-ethylhexylthio group, 3,5,5-trimethylhexylthio group, decalylthiogroup, methoxyethylthio group, ethoxyethylthio group,methoxyethoxyethylthio group, ethoxyethoxyethylthio group andn-decylthio group.

Examples of the substituted or unsubstituted aralkylthio groups used forR¹ to R¹⁶ are aralkylthio groups which may have the substituents similarto the above-mentioned alkyl groups, and are preferably aralkylthiogroups of 7 to 15 in carbon number and the like, such as benzylthiogroup, nitrobenzylthio group, cyanobenzylthio group, hydroxybenzylthiogroup, methylbenzylthio group, trifluoromethylbenzylthio group,naphthylmethylthio group, nitronaphthylmethylthio group,cyanonaphthylmethylthio group, hydroxynaphthylmethylthio group,methylnaphthylmethylthio group, trifluoromethylnaphthylmethylthio groupand fluorene-9-ylethylthio group.

Examples of the substituted or unsubstituted arylthio groups used for R¹to R¹⁶ are arylthio groups which may have the substituents similar tothe above-mentioned alkyl groups, and are preferably arylthio groups of6 to 18 in carbon number, such as phenylthio group, 2-methylphenylthiogroup, 4-methylphenylthio group, 4-t-butylphenylthio group,2-methoxyphenylthio group, 4-iso-propylphenylthio group, tolylthiogroup, naphthylthio group, ferrocenylthio group, cobaltcenylthio group,nickelocenylthio group, octamethylferrocenylthio group,octamethylcobaltcenylthio group and octamethylnickelocenylthio group.

Also, as examples of substituted or unsubstituted heteroarylthio groupsused for R¹ to R¹⁶, which are arylthio groups having oxygen atoms,substituted or unsubstituted sulfur atoms, and substituted orunsubstituted nitrogen atoms between carbon atoms, heteroarylthio groupsmade by the aforementioned heteroaryl groups bonding with oxygen atomscan be mentioned.

Examples of the substituted or unsubstituted alkenylthio groups used forR¹ to R¹⁶ are alkenylthio groups which may have the substituents similarto the above-mentioned alkyl groups, and are preferably alkenylthiogroups of 2 to 10 in carbon number, such as vinylthio group,propenylthio group, 1-butenylthio group, iso-butenylthio group,1-pentenylthio group, 2-pentenylthio group, 2-methyl-1-butenylthiogroup, 3-methyl-1-butenylthio group, 2-methyl-2-butenylthio group,cyclopentadienylthio group, 2,2-dicyanovinylthio group,2-cyano-2-methylcarboxylvinylthio group, 2-cyano-2-methylsulfonvinylthiogroup, styrylthio group, 4-phenyl-2-butenylthio group and cinnamylalkoxygroup.

Also, as the substituted hydrocarbonthio groups shown by R¹ to R¹⁶,oxo-substituted hydrocarbonthio groups whose carbon atoms directlylinked to sulfur atoms directly linked to azaannulene rings can bementioned. As specific examples, substituted or unsubstituted acylthiogroups; substituted or unsubstituted hydrocarbonoxycarbonylthio groupssuch as alkoxycarbonylthio group, aralkyloxycarbonylthio group,aryloxycarbonylthio group and alkenyloxycarbonylthio group; substitutedor unsubstituted hydrocarbonaminocarbonylthio groups such asmonosubstituted aminocarbonylthio group and disubstitutedaminocarbonylthio group; and the like can be mentioned.

Examples of the substituted or unsubstituted acylthio groups used for R¹to R¹⁶ are acylthio groups which may have the substituents similar tothe above-mentioned alkyl groups, and are preferably acylthio groups of1 to 15 in carbon number, such as formylthio group, methylcarbonylthiogroup, ethylcarbonylthio group, n-propylcarbonylthio group,iso-propylcarbonylthio group, n-butylcarbonylthio group,iso-butylcarbonylthio group, sec-butylcarbonylthio group,t-butylcarbonylthio group, n-pentylcarbonylthio group,iso-pentylcarbonylthio group, neopentylcarbonylthio group,2-methylbutylcarbonylthio group, benzoylthio group, methylbenzoylthiogroup, ethylbenzoylthio group, tolylcarbonylthio group,propylbenzoylthio group, 4-t-butylbenzoylthio group,nitrobenzylcarbonylthio group, 3-butoxy-2-naphthoylthio group,cinnamoylthio group, ferrocenecarbonylthio group and1-methylferrocene-1′-carbonylthio group.

Examples of the substituted or unsubstituted alkoxycarbonylthio groupsused for R¹ to R¹⁶ are alkoxycarbonylthio groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably: alkoxycarbonylthio groups of 2 to 11 in carbon number, suchas methoxycarbonylthio group, ethoxycarbonylthio group,n-propoxycarbonylthio group, iso-propoxycarbonylthio group,n-butoxycarbonylthio group, iso-butoxycarbonylthio group,sec-butoxycarbonylthio group, t-butoxycarbonylthio group,n-pentoxycarbonylthio group, iso-pentoxycarbonylthio group,neopentoxycarbonylthio group, 2-pentoxycarbonylthio group,2-ethylhexyloxycarbonylthio group, 3,5,5-trimethylhexyloxycarbonylthiogroup, decalyloxycarbonylthio group, cyclohexyloxycarbonylthio group,chloroethoxycarbonylthio group, hydroxymethoxycarbonylthio group andhydroxyethoxycarbonylthio group;

alkylthio-substituted alkoxycarbonylthio groups of 3 to 11 in carbonnumber, such as methoxymethoxycarbonylthio group,methoxyethoxycarbonylthio group, ethoxyethoxycarbonylthio group,propoxyethoxycarbonylthio group, butoxyethoxycarbonylthio group,pentoxyethoxycarbonylthio group, hexyloxyethoxycarbonylthio group,butoxybutoxycarbonylthio group, hexyloxybutoxycarbonylthio group,hydroxymethoxymethoxycarbonylthio group andhydroxyethoxyethoxycarbonylthio group;

alkoxyalkoxy-substituted alkoxycarbonylthio groups of 4 to 11 in carbonnumber, such as methoxymethoxymethoxycarbonylthio group,methoxyethoxyethoxycarbonylthio group, ethoxyethoxyethoxycarbonylthiogroup, propoxyethoxyethoxycarbonylthio group,butoxyethoxyethoxycarbonylthio group, pentoxyethoxyethoxycarbonylthiogroup and hexyloxyethoxyethoxycarbonylthio group;

metallocenyl-substituted alkoxycarbonylthio groups of 11 to 20 in carbonnumber, such as ferrocenylmethoxycarbonylthio group,ferrocenylethoxycarbonylthio group, ferrocenylpropoxycarbonylthio group,ferrocenylbutoxycarbonylthio group, ferrocenylpentyloxycarbonylthiogroup, ferrocenylhexyloxycarbonylthio group,ferrocenylheptyloxycarbonylthio group, ferrocenyloctyloxycarbonylthiogroup, ferrocenylnonyloxycarbonylthio group,ferrocenyldecyloxycarbonylthio group;

cobaltcenylmethoxycarbonylthio group, cobaltcenylethoxycarbonylthiogroup,

nickelocenylmethoxycarbonylthio group, nickelocenylethoxycarbonylthiogroup,

dichlorotitanocenylmethoxycarbonylthio group,trichlorotitaniumcyclopentadienylmethoxycarbonylthio group,bis(trifluoromethanesulfonato)titanocenemethoxycarbonylthio group,dichlorozirconocenylmethoxycarbonylthio group,dimethylzirconocenylmethoxycarbonylthio group,diethoxyzirconocenylmethoxycarbonylthio group,bis(cyclopentadienyl)chromiummethoxycarbonylthio group,bis(cyclopentadienyl)dichlorohafniummethoxycarbonylthio group,bis(cyclopentadienyl)dichloroniobiummethoxycarbonylthio group,bis(cyclopentadienyl)rutheniummethoxycarbonylthio group,bis(cyclopentadienyl)vanadiummethoxycarbonylthio group,bis(cyclopentadienyl)dichlorovanadiummethoxycarbonylthio group andbis(cyclopentadienyl)osmiummethoxycarbonylthio group; and the like.

Examples of the substituted or unsubstituted aralkyloxycarbonylthiogroups used for R¹ to R¹⁶ are aralkyloxycarbonylthio groups which mayhave the substituents similar to the above-mentioned alkyl groups, andare preferably aralkyloxycarbonylthio groups of 8 to 16 in carbon numberand the like, such as benzyloxycarbonylthio group,nitrobenzyloxycarbonylthio group, cyanobenzyloxycarbonylthio group,hydroxybenzyloxycarbonylthio group, methylbenzyloxycarbonylthio group,trifluoromethylbenzyloxycarbonylthio group, naphthylmethoxycarbonylthiogroup, nitronaphthylmethoxycarbonylthio group,cyanonaphthylmethoxycarbonylthio group,hydroxynaphthylmethoxycarbonylthio group,methylnaphthylmethoxycarbonylthio group,trifluoromethylnaphthylmethoxycarbonylthio group andfluorene-9-ylethoxycarbonylthio group.

Examples of the substituted or unsubstituted aryloxycarbonylthio groupsused for R¹ to R¹⁶ are aryloxycarbonylthio groups which may have thesubstituents similar to the above-mentioned aryl groups, and arepreferably aryloxycarbonylthio groups of 7 to 11 in carbon number, suchas phenoxycarbonylthio group, 2-methylphenoxycarbonylthio group,4-methylphenoxycarbonylthio group, 4-t-butylphenoxycarbonylthio group,2-methoxyphenoxycarbonylthio group, 4-iso-propylphenoxycarbonylthiogroup, naphthoxycarbonylthio group, ferrocenyloxycarbonylthio group,cobaltcenyloxycarbonylthio group, nickelocenyloxycarbonylthio group,zirconocenyloxycarbonylthio group, octamethylferrocenyloxycarbonylthiogroup, octamethylcobaltcenyloxycarbonylthio group,octamethylnickelocenyloxycarbonylthio group andoctamethylzirconocenyloxycarbonylthio group.

Examples of the substituted or unsubstituted alkenyloxycarbonylthiogroups used for R¹ to R¹⁶ are alkenyloxycarbonylthio groups which mayhave the substituents similar to the above-mentioned alkyl groups, andare preferably alkenyloxycarbonylthio groups of 3 to 11 in carbonnumber, such as vinyloxycarbonylthio group, propenyloxycarbonylthiogroup, 1-butenyloxycarbonylthio group, iso-butenyloxycarbonylthio group,1-pentenyloxycarbonylthio group, 2-pentenyloxycarbonylthio group,cyclopentadienyloxycarbonylthio group, 2-methyl-1-butenyloxycarbonylthiogroup, 3-methyl-1-butenyloxycarbonylthio group,2-methyl-2-butenyloxycarbonylthio group, 2,2-dicyanovinyloxycarbonylthiogroup, 2-cyano-2-methylcarboxylvinyloxycarbonylthio group,2-cyano-2-methylsulfonvinyloxycarbonylthio group, styryloxycarbonylthiogroup and 4-phenyl-2-butenyloxycarbonylthio group.

Examples of the monosubstituted aminocarbonylthio groups used for R¹ toR¹⁶ are monosubstituted aminocarbonylthio groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably: monoalkylaminocarbonylthio groups of 2 to 11 in carbonnumber, such as methylaminocarbonylthio group, ethylaminocarbonylthiogroup, propylaminocarbonylthio group, butylaminocarbonylthio group,pentylaminocarbonylthio group, hexylaminocarbonylthio group,heptylaminocarbonylthio group, octylaminocarbonylthio group,(2-ethylhexyl)aminocarbonylthio group, cyclohexylaminocarbonylthiogroup, (3,5,5-trimethylhexyl)aminocarbonylthio group,nonylaminocarbonylthio group and decylaminocarbonylthio group;

monoaralkylaminocarbonylthio groups of 8 to 11 in carbon number, such asbenzylaminocarbonylthio group, phenethylaminocarbonylthio group,(3-phenylpropylaminocarbonylthio group, (4-ethylbenzyl)aminocarbonylthiogroup, (4-isopropylbenzyl)aminocarbonylthio group,(4-methylbenzyl)aminocarbonylthio group,(4-ethylbenzyl)aminocarbonylthio group, (4-allylbenzyl)aminocarbonylthiogroup, [4-(2-cyanoethyl)benzyl]aminocarbonylthio group and[4-(2-acetoxyethyl)benzyl]aminocarbonylthio group;

monoarylaminocarbonylthio groups of 7 to 11 in carbon number, such asanilinocarbonylthio group, naphthylaminocarbonylthio group,toluidinocarbonylthio group, xylidinocarbonylthio group,ethylanilinocarbonylthio group, isopropylanilinocarbonylthio group,methoxyanilinocarbonylthio group, ethoxyanilinocarbonylthio group,chloroanilinocarbonylthio group, acetylanilinocarbonylthio group,methoxycarbonylanilinocarbonylthio group,ethoxycarbonylanilinocarbonylthio group,propoxycarbonylanilinocarbonylthio group, 4-methylanilinocarbonylthiogroup and 4-ethylanilinocarbonylthio group;

monoalkenylaminocarbonylthio groups of 3 to 11 in carbon number, such asvinylaminocarbonylthio group, allylaminocarbonylthio group,butenylaminocarbonylthio group, pentenylaminocarbonylthio group,hexenylaminocarbonylthio group, cyclohexenylaminocarbonylthio group,octadienylaminocarbonylthio group and adamantenylaminocarbonylthiogroup; and the like.

Examples of the disubstituted aminocarbonylthio groups used for R¹ toR¹⁶ are disubstituted aminocarbonylthio groups which may have thesubstituents similar to the above-mentioned alkyl groups, and arepreferably: dialkylaminocarbonylthio groups of 3 to 17 in carbon number,such as dimethylaminocarbonylthio group, diethylaminocarbonylthio group,methylethylaminocarbonylthio group, dipropylaminocarbonylthio group,dibutylaminocarbonylthio group, di-n-hexylaminocarbonylthio group,dicyclohexylaminocarbonylthio group, dioctylaminocarbonylthio group,pyrrolidinocarbonylthio group, piperidinocarbonylthio group,morpholinocarbonylthio group, bis(methoxyethyl)aminocarbonylthio group,bis(ethoxyethyl)aminocarbonylthio group,bis(propoxyethyl)aminocarbonylthio group,bis(butoxyethyl)aminocarbonylthio group,di(acetyloxyethyl)aminocarbonylthio group,di(hydroxyethyl)aminocarbonylthio group,N-ethyl-N-(2-cyanoethyl)aminocarbonylthio group anddi(propionyloxyethyl)aminocarbonylthio group;

diaralkylaminocarbonylthio groups of 15 to 21 in carbon number, such asdibenzylaminocarbonylthio group, diphenethylaminocarbonylthio group,bis(4-ethylbenzyl)aminocarbonylthio group andbis(4-isopropylbenzyl)aminocarbonylthio group;

diarylaminocarbonylthio groups of 13 to 15 in carbon number, such asdiphenylaminocarbonylthio group, ditolylaminocarbonylthio group andN-phenyl-N-tolylaminocarbonylthio group;

dialkenylaminocarbonylthio groups of 5 to 13 in carbon number, such asdivinylaminocarbonylthio group, diallylaminocarbonylthio group,dibutenylaminocarbonylthio group, dipentenylaminocarbonylthio group,dihexenylaminocarbonylthio group and N-vinyl-N-allylaminocarbonylthiogroup;

and disubstituted aminocarbonylthio groups of 4 to 11 in carbon numbercontaining substituents selected from substituted or unsubstituted alkylgroups, aralkyl groups, aryl groups and alkenyl groups, such asN-phenyl-N-allylaminocarbonylthio group,N-(2-acetyloxyethyl)-N-ethylaminocarbonylthio group,N-tolyl-N-methylaminocarbonylthio group,N-vinyl-N-methylaminocarbonylthio group andN-benzyl-N-allylaminocarbonylthio group.

As specific examples of the substituted or unsubstituted amino groupsshown by R¹ to R¹⁶: unsubstituted amino groups; and monosubstitutedamino groups and disubstituted amino groups, which may have oxygenatoms, substituted or unsubstituted sulfur atoms, and substituted orunsubstituted nitrogen atoms between carbon atoms, can be mentioned.

Examples of the monosubstituted amino groups used for R¹ to R¹⁶ aremonosubstituted amino groups which may have the substituents similar tothe above-mentioned alkyl groups, and are preferably the followingmonoalkylamino groups: normal chain, branched-chain or cyclicunsubstituted monoalkylamino groups of 1 to 15 in carbon number, such asmethylamino group, ethylamino group, n-propylamino group, isopropylaminogroup, n-butylamino group, isobutylamino group, tert-butylamino group,sec-butylamino group, n-pentylamino group, isopentylamino group,tert-pentylamino group, sec-pentylamino group, cyclopentylamino group,n-hexylamino group, 1-methylpentylamino group, 2-methylpentylaminogroup, 3-methylpentylamino group, 4-methylpentylamino group,1,1-dimethylbutylamino group, 1,2-dimethylbutylamino group,1,3-dimethylbutylamino group, 2,3-dimethylbutylamino group,1,1,2-trimethylpropylamino group, 1,2,2-trimethylpropylamino group,1-ethylbutylamino group, 2-ethylbutylamino group,1-ethyl-2-methylpropylamino group, cyclohexylamino group,methylcyclopentylamino group, n-heptylamino group, 1-methylhexylaminogroup, 2-methylhexylamino group, 3-methylhexylamino group,4-methylhexylamino group, 5-methylhexylamino group, dimethylpentylaminogroup, 1-ethylpentylamino group, 2-ethylpentylamino group,3-ethylpentylamino group, trimethylbutylamino group,1-ethyl-1-methylbutylamino group, 1-ethyl-2-methylbutylamino group,1-ethyl-3-methylbutylamino group, 2-ethyl-1-methylbutylamino group,2-ethyl-3-methylbutylamino group, 1-n-propylbutylamino group,1-isopropylbutylamino group, 1-isopropyl-2-methylpropylamino group,methylcyclohexylamino group, n-octylamino group, 1-methylheptylaminogroup, 2-methylheptylamino group, 3-methylheptylamino group,4-methylheptylamino group, 5-methylheptylamino group,6-methylheptylamino group, dimethylhexylamino group, 1-ethylhexylaminogroup, 2-ethylhexylamino group, 3-ethylhexylamino group,4-ethylhexylamino group, 1-n-propylpentylamino group,2-n-propylpentylamino group, 1-isopropylpentylamino group,2-isopropylpentylamino group, 1-ethyl-1-methylpentylamino group,1-ethyl-2-methylpentylamino group, 1-ethyl-3-methylpentylamino group,1-ethyl-4-methylpentylamino group, 2-ethyl-1-methylpentylamino group,2-ethyl-2-methylpentylamino group, 2-ethyl-3-methylpentylamino group,2-ethyl-4-methylpentylamino group, 3-ethyl-1-methylpentylamino group,3-ethyl-2-methylpentylamino group, 3-ethyl-3-methylpentylamino group,3-ethyl-4-methylpentylamino group, trimethylpentylamino group,1-n-butylbutylamino group, 1-isobutylbutylamino group,1-sec-butylbutylamino group, 1-tert-butylbutylamino group,2-tert-butylbutylamino group, 1-n-propyl-1-methylbutylamino group,1-n-propyl-2-methylbutylamino group, 1-n-propyl-3-methylbutylaminogroup, 1-isopropyl-1-methylbutylamino group,1-isopropyl-2-methylbutylamino group, 1-isopropyl-3-methylbutylaminogroup, 1,1-diethylbutylamino group, 1,2-diethylbutylamino group,1-ethyl-1,2-dimethylbutylamino group, 1-ethyl-1,3-dimethylbutylaminogroup, 1-ethyl-2,3-dimethylbutylamino group,2-ethyl-1,1-dimethylbutylamino group, 2-ethyl-1,2-dimethylbutylaminogroup, 2-ethyl-1,3-dimethylbutylamino group,2-ethyl-2,3-dimethylbutylamino group, 1,1,3,3-tetramethylbutylaminogroup, 1,2-dimethylcyclohexylamino group, 1,3-dimethylcyclohexylaminogroup, 1,4-dimethylcyclohexylamino group, ethylcyclohexylamino group,n-nonylamino group, 3,5,5-trimethylhexylamino group, n-decylamino group,n-undecylamino group, n-dodecylamino group, 1-adamantylamino group andn-pentadecylamino group;

alkoxy-substituted monoalkylamino groups of 2 to 15 in carbon number,such as methoxymethylamino group, methoxyethylamino group,ethoxyethylamino group, n-propoxyethylamino group, isopropoxyethylaminogroup, n-butoxyethylamino group, isobutoxyethylamino group,tert-butoxyethylamino group, sec-butoxyethylamino group,n-pentyloxyethylamino group, isopentyloxyethylamino group,tert-pentyloxyethylamino group, sec-pentyloxyethylamino group,cyclopentyloxyethylamino group, n-hexyloxyethylamino group,ethylcyclohexyloxyethylamino group, n-nonyloxyethylamino group,(3,5,5-trimethylhexyloxy)ethylamino group,(3,5,5-trimethylhexyloxy)butylamino group, n-decyloxyethylamino group,n-undecyloxyethylamino group, n-dodecyloxyethylamino group,3-methoxypropylamino group, 3-ethoxypropylamino group,3-(n-propoxy)propylamino group, 2-isopropoxypropylamino group,2-methoxybutylamino group, 2-ethoxybutylamino group,2-(n-propoxy)butylamino group, 4-isopropoxybutylamino group,decalyloxyethylamino group and adamantyloxyethylamino group;

alkoxyalkoxy-substituted normal chain, branched-chain or cyclicmonoalkylamino groups of 3 to 15 in carbon number, such asmethoxymethoxymethylamino group, ethoxymethoxymethylamino group,propoxymethoxymethylamino group, butoxymethoxymethylamino group,methoxyethoxymethylamino group, ethoxyethoxymethylamino group,propoxyethoxymethylamino group, butoxyethoxymethylamino group,methoxypropoxymethylamino group, ethoxypropoxymethylamino group,propoxypropoxymethylamino group, butoxypropoxymethylamino group,methoxybutoxymethylamino group, ethoxybutoxymethylamino group,propoxybutoxymethylamino group, butoxybutoxymethylamino group,methoxymethoxyethylamino group, ethoxymethoxyethylamino group,propoxymethoxyethylamino group, butoxymethoxyethylamino group,methoxyethoxyethylamino group, ethoxyethoxyethylamino group,propoxyethoxyethylamino group, butoxyethoxyethylamino group,methoxypropoxyethylamino group, ethoxypropoxyethylamino group,propoxypropoxyethylamino group, butoxypropoxyethylamino group,methoxybutoxyethylamino group, ethoxybutoxyethylamino group,propoxybutoxyethylamino group, butoxybutoxyethylamino group,methoxymethoxypropylamino group, ethoxymethoxypropylamino group,propoxymethoxypropylamino group, butoxymethoxypropylamino group,methoxyethoxypropylamino group, ethoxyethoxypropylamino group,propoxyethoxypropylamino group, butoxyethoxypropylamino group,methoxypropoxypropylamino group, ethoxypropoxypropylamino group,propoxypropoxypropylamino group, butoxypropoxypropylamino group,methoxybutoxypropylamino group, ethoxybutoxypropylamino group,propoxybutoxypropylamino group, butoxybutoxypropylamino group,methoxymethoxybutylamino group, ethoxymethoxybutylamino group,propoxymethoxybutylamino group, butoxymethoxybutylamino group,methoxyethoxybutylamino group, ethoxyethoxybutylamino group,propoxyethoxybutylamino group, butoxyethoxybutoxy group,methoxypropoxybutylamino group, ethoxypropoxybutylamino group,propoxypropoxybutylamino group, butoxypropoxybutylamino group,methoxybutoxybutylamino group, ethoxybutoxybutylamino group,propoxybutoxybutylamino group, butoxybutoxybutylamino group,(4-ethylcyclohexyloxy)ethoxyethylamino group,(2-ethyl-1-hexyloxy)ethoxypropylamino group and[4-(3,5,5-trimethylhexyloxy)butoxy]ethylamino group;

alkoxycarbonyl-substituted monoalkylamino groups of 3 to 10 in carbonnumber, such as methoxycarbonylmethylamino group,ethoxycarbonylmethylamino group, n-propoxycarbonylmethylamino group,isopropoxycarbonylmethylamino group and(4′-ethylcyclohexyloxy)carbonylmethylamino group;

acyl-substituted monoalkylamino groups of 3 to 10 in carbon number, suchas acetylmethylamino group, ethylcarbonylmethylamino group,octylcarbonylmethylamino group and phenacylamino group;

acylamino-substituted monoalkylamino groups of 3 to 10 in carbon number,such as acetyloxymethylamino group, acetyloxyethylamino group,acetyloxyhexylamino group and butanoyloxycyclohexylamino group;

monoalkylamino-substituted monoalkylamino groups of 2 to 10 in carbonnumber, such as methylaminomethylamino group, 2-methylaminoethylaminogroup, 2-(2-methylaminoethoxy)ethylamino group, 4-methylaminobutylaminogroup, 1-methylaminopropane-2-ylamino group, 3-methylaminopropylaminogroup, 2-methylamino-2-methylpropylamino group, 2-ethylaminoethylaminogroup, 2-(2-ethylaminoethoxy)ethylamino group, 3-ethylaminopropylaminogroup, 1-ethylaminopropylamino group, 2-isopropylaminoethylamino group,2-(n-butylamino)ethylamino group, 3-(n-hexylamino)propylamino group and4-(cyclohexylamino)butylamino group;

alkylaminomonoalkylamino-substituted monoalkylamino groups of 3 to 10 incarbon number, such as methylaminomethoxymethylamino group,methylaminoethoxyethylamino group, methylaminoethoxypropylamino group,ethylaminoethoxypropylamino group and4-(2′-isobutylaminopropoxy)butylamino group;

dimonoalkylamino-substituted monoalkylamino groups of 3 to 15 in carbonnumber, such as dimethylaminomethylamino group,2-dimethylaminoethylamino group, 2-(2-dimethylaminoethoxy)ethylaminogroup, 4-dimethylaminobutylamino group, 1-dimethylaminopropane-2-ylaminogroup, 3-dimethylaminopropylamino group,2-dimethylamino-2-methylpropylamino group, 2-diethylaminoethylaminogroup, 2-(2-diethylaminoethoxy)ethylamino group,3-diethylaminopropylamino group, 1-diethylaminopropylamino group,2-diisopropylaminoethylamino group, 2-(di-n-butylamino)ethylamino group,2-piperidylethylamino group and 3-(di-n-hexylamino)propylamino group;

dialkylaminomonoalkylamino-substituted monoalkylamino groups of 4 to 15in carbon number, such as dimethylaminomethoxymethylamino group,dimethylaminoethoxyethylamino group, dimethylaminoethoxypropylaminogroup, diethylaminoethoxypropylamino group and4-(2′-diisobutylaminopropoxy)butylamino group;

monoalkylamino-substituted monoalkylamino groups of 2 to 15 in carbonnumber, such as methylthiomethylamino group, 2-methylthioethylaminogroup, 2-ethylthioethylamino group, 2-n-propylthioethylamino group,2-isopropylthioethylamino group, 2-n-butylthioethylamino group,2-isobutylthioethylamino group and (3,5,5-trimethylhexylthio)hexylaminogroup;

and the like; more preferably the following monosubstituted aminogroups: monoalkylamino groups of 1 to 10 in carbon number, such asmethylamino group, ethylamino group, n-propylamino group,iso-propylamino group, n-butylamino group, iso-butylamino group,sec-butylamino group, t-butylamino group, n-pentylamino group,iso-pentylamino group, neopentylamino group, 2-methylbutylamino group,n-hexylamino group, n-heptylamino group, n-octylamino group,2-ethylhexylamino group, 3,5,5-trimethylhexylamino group, decalylaminogroup, methoxyethylamino group, ethoxyethylamino group,methoxyethoxyethylamino group, ethoxyethoxyethylamino group andn-decylamino group;

monoaralkylamino groups of 7 to 10 in carbon number, such as benzylaminogroup, phenethylamino group, (3-phenylpropyl)amino group,(4-ethylbenzyl)amino group, (4-isopropylbenzyl)amino group,(4-methylbenzyl)amino group, (4-ethylbenzyl)amino group,(4-allylbenzyl)amino group, [4-(2-cyanoethyl)benzyl]amino group and[4-(2-acetoxyethyl)benzyl]amino group;

monoarylamino groups of 6 to 10 in carbon number, such as anilino group,naphthylamino group, toluidino group, xylidino group, ethylanilinogroup, isopropylanilino group, methoxyanilino group, ethoxyanilinogroup, chloroanilino group, acetylanilino group, methoxycarbonylanilinogroup, ethoxycarbonylanilino group, propoxycarbonylanilino group,4-methylanilino group, 4-ethylanilino group, ferrocenylamino group,cobaltcenylamino group, nickelocenylamino group, zirconocenylaminogroup, octamethylferrocenylamino group, octamethylcobaltcenylaminogroup, octamethylnickelocenylamino group and octamethylzirconocenylaminogroup;

monoalkenylamino groups of 2 to 10 in carbon number, such as vinylaminogroup, allylamino group, butenylamino group, pentenylamino group,hexenylamino group, cyclohexenylamino group, cyclopentadienylaminogroup, octadienylamino group and adamantenylamino group;

acylamino groups of 1 to 16 in carbon number, such as formylamino group,methylcarbonylamino group, ethylcarbonylamino group,n-propylcarbonylamino group, iso-propylcarbonylamino group,n-butylcarbonylamino group, iso-butylcarbonylamino group,sec-butylcarbonylamino group, t-butylcarbonylamino group,n-pentylcarbonylamino group, iso-pentylcarbonylamino group,neopentylcarbonylamino group, 2-methylbutylcarbonylamino group,benzoylamino group, methylbenzoylamino group, ethylbenzoylamino group,tolylcarbonylamino group, propylbenzoylamino group,4-t-butylbenzoylamino group, nitrobenzylcarbonylamino group,3-butoxy-2-naphthoylamino group, cinnamoylamino group,ferrocenecarbonylamino group, 1-methylferrocene-1′-carbonylamino group,cobaltcenecarbonylamino group and nickelocenecarbonylamino group; andthe like.

Examples of the disubstituted amino groups used for R¹ to R¹⁶ aredisubstituted amino groups which may have the substituents similar tothe above-mentioned alkyl groups, and are preferably: normal chain,branched-chain or cyclic unsubstituted dialkylamino groups of 1 to 15 incarbon number, such as dimethylamino group, diethylamino group,di(n-propyl)amino group, di(isopropyl)amino group, di (n-butyl) aminogroup, di (isobutyl) amino group, di (tert-butyl)amino group,di(sec-butyl)amino group, di(n-pentyl)amino group, di(isopentyl)aminogroup, di(tert-pentyl)amino group, di(sec-pentyl)amino group, di(cyclopentyl) amino group, di (n-hexyl) amino group, di(1-methylpentyl)amino group, di(2-methylpentyl)amino group,di(3-methylpentyl)amino group, di(4-methylpentyl)amino group,di(1,1-dimethylbutyl)amino group, di(1,2-dimethylbutyl)amino group,di(1,3-dimethylbutyl)amino group, di(2,3-dimethylbutyl)amino group,di(1,1,2-trimethylpropyl)amino group, di(1,2,2-trimethylpropyl)aminogroup, di(1-ethylbutyl)amino group, di(2-ethylbutyl) amino group,di(1-ethyl-2-methylpropyl)amino group, di(cyclohexyl)amino group,di(methylcyclopentyl)amino group, di(n-heptyl)amino group,di(1-methylhexyl)amino group, di(2-methylhexyl)amino group,di(3-methylhexyl)amino group, di(4-methylhexyl)amino group,di(5-methylhexyl)amino group, di(dimethylpentyl)amino group,di(1-ethylpentyl)amino group, di(2-ethylpentyl)amino group,di(3-ethylpentyl)amino group, di(trimethylbutyl)amino group,di(1-ethyl-1-methylbutyl)amino group, di(1-ethyl-2-methylbutyl)aminogroup, di(1-ethyl-3-methylbutyl)amino group,di(2-ethyl-1-methylbutyl)amino group, di(2-ethyl-3-methylbutyl)aminogroup, di(1-n-propylbutyl)amino group, di(1-isopropylbutyl)amino group,di(1-isopropyl-2-methylpropyl) amino group, di (methylcyclohexyl) aminogroup, di(n-octyl)amino group, di(1-methylheptyl)amino group,di(2-methylheptyl)amino group, di(3-methylheptyl)amino group,di(4-methylheptyl)amino group, di(5-methylheptyl)amino group,di(6-methylheptyl)amino group, di (dimethylhexyl) amino group, di(1-ethylhexyl) amino group, di(2-ethylhexyl)amio group,di(3-ethylhexyl)amino group, di(4-ethylhexyl)amino group,di(1-n-propylpentyl)amino group, di(2-n-propylpentyl)amino group,di(1-isopropylpentyl)amino group, di(2-isopropylpentyl)amino group,di(1-ethyl-1-methylpentyl)amino group, di(1-ethyl-2-methylpentyl)aminogroup, di(1-ethyl-3-methylpentyl)amino group,di(1-ethyl-4-methylpentyl)amino group, di(2-ethyl-1-methylpentyl)aminogroup, di(2-ethyl-2-methylpentyl)amino group,di(2-ethyl-3-methylpentyl)amino group, di(2-ethyl-4-methylpentyl)aminogroup, di(3-ethyl-1-methylpentyl)amino group,di(3-ethyl-2-methylpentyl)amino group, di(3-ethyl-3-methylpentyl)aminogroup, di(3-ethyl-4-methylpentyl)amino group, di(trimethylpentyl)aminogroup, di(1-n-butylbutyl)amino group, di(1-isobutylbutyl)amino group,di(1-sec-butylbutyl)amino group, di(1-tert-butylbutyl)amino group,di(2-tert-butylbutyl)amino group, di(1-n-propyl-1-methylbutyl) aminogroup, di(1-n-propyl-2-methylbutyl) amino group,di(1-n-propyl-3-methylbutyl)amino group,di(1-isopropyl-1-methylbutyl)amino group,di(1-isopropyl-2-methylbutyl)amino group,di(1-isopropyl-3-methylbutyl)amino group, di(1,1-diethylbutyl)aminogroup, di(1,2-diethylbutyl)amino group,di(1-ethyl-1,2-dimethylbutyl)amino group,di(1-ethyl-1,3-dimethylbutyl)amino group,di(1-ethyl-2,3-dimethylbutyl)amino group,di(2-ethyl-1,1-dimethylbutyl)amino group,di(2-ethyl-1,2-dimethylbutyl)amino group,di(2-ethyl-1,3-dimethylbutyl)amino group,di(2-ethyl-2,3-dimethylbutyl)amino group,di(1,1,3,3-tetramethylbutyl)amino group, di(1,2-dimethylcyclohexyl)aminogroup, di(1,3-dimethylcyclohexyl)amino group,di(1,4-dimethylcyclohexyl)amino group, di(ethylcyclohexyl)amino group,di(n-nonyl)amino group, di(3,5,5-trimethylhexyl)amino group,di(n-decyl)amino group, di(n-undecyl)amino group, di(n-dodecyl)aminogroup, di(1-adamantyl)amino group and di(n-pentadecyl)amino group;

alkoxy-substituted dialkylamino groups of 2 to 15 in carbon number, suchas di(methoxymethyl)amino group, di(methoxyethyl)amino group,di(ethoxyethyl)amino group, di (n-propoxyethyl) amino group, di(isopropoxyethyl) amino group, di(n-butoxyethyl)amino group,di(isobutoxyethyl)amino group, di(tert-butoxyethyl)amino group,di(sec-butoxyethyl)amino group, di(n-pentyloxyethyl)amino group,di(isopentyloxyethyl)amino group, di(tert-pentyloxyethyl)amino group,di(sec-pentyloxyethyl)amino group, di(cyclopentyloxyethyl)amino group,di(n-hexyloxyethyl)amino group, di(ethylcyclohexyloxyethyl)amino group,di(n-nonyloxyethyl)amino group, di[(3,5,5-trimethylhexyloxy)ethyl]aminogroup, di[(3,5,5-trimethylhexyloxy)butyl]amino group,di(n-decyloxyethyl)amino group, di(n-undecyloxyethyl)amino group, di(n-dodecyloxyethyl) amino group, di (3-methoxypropyl) amino group,di(3-ethoxypropyl)amino group, di[3-(n-propoxy)propyl]amino group,di(2-isopropoxypropyl)amino group, di(2-methoxybutyl)amino group,di(2-ethoxybutyl)amino group, di[2-(n-propoxy)butyl]amino group, di(4-isopropoxybutyl) amino group, di (decalyloxyethyl) amino group anddi(adamantyloxyethyl)amino group;

alkoxyalkoxy-substituted normal chain, branched-chain, cyclicdialkylamino groups of 3 to 15 in carbon number, such as(methoxymethoxymethyl)amino group, di(ethoxymethoxymethyl)amino group,di(propoxymethoxymethyl)amino group, di(butoxymethoxymethyl)amino group,di(methoxyethoxymethyl)amino group, di(ethoxyethoxymethyl)amino group,di(propoxyethoxymethyl)amino group, di(butoxyethoxymethyl)amino group,di(methoxypropoxymethyl)amino group, di(ethoxypropoxymethyl)amino group,di(propoxypropoxymethyl)amino group, di(butoxypropoxymethyl)amino group,di(methoxybutoxymethyl)amino group, di(ethoxybutoxymethyl)amino group,di(propoxybutoxymethyl)amino group, di(butoxybutoxymethyl)amino group,di(methoxymethoxyethyl)amino group, di(ethoxymethoxyethyl)amino group,di(propoxymethoxyethyl)amino group, di(butoxymethoxyethyl)amino group,di(methoxyethoxyethyl)amino group, di(ethoxyethoxyethyl)amino group,di(propoxyethoxyethyl)amino group, di(butoxyethoxyethyl)amino group,di(methoxypropoxyethyl)amino group, di(ethoxypropoxyethyl)amino group,di(propoxypropoxyethyl)amino group, di(butoxypropoxyethyl)amino group,di(methoxybutoxyethyl)amino group, di(ethoxybutoxyethyl)amino group,di(propoxybutoxyethyl)amino group, di(butoxybutoxyethyl)amino group,di(methoxymethoxypropyl)amino group, di(ethoxymethoxypropyl)amino group,di(propoxymethoxypropyl)amino group, di(butoxymethoxypropyl)amino group,di(methoxyethoxypropyl)amino group, di(ethoxyethoxypropyl)amino group,di(propoxyethoxypropyl)amino group, di(butoxyethoxypropyl)amino group,di(methoxypropoxypropyl)amino group, di(ethoxypropoxypropyl)amino group,di(propoxypropoxypropyl)amino group, di(butoxypropoxypropyl)amino group,di(methoxybutoxypropyl)amino group, di(ethoxybutoxypropyl)amino group,di(propoxybutoxypropyl)amino group, di(butoxybutoxypropyl)amino group,di(methoxymethoxybutyl)amino group, di(ethoxymethoxybutyl)amino group,di(propoxymethoxybutyl)amino group, di(butoxymethoxybutyl)amino group,di(methoxyethoxybutyl)amino group, di(ethoxyethoxybutyl)amino group,di(propoxyethoxybutyl)amino group, di(butoxyethoxybutoxy,methoxypropoxybutyl)amino group, di(ethoxypropoxybutyl)amino group,di(propoxypropoxybutyl)amino group, di(butoxypropoxybutyl)amino group,di(methoxybutoxybutyl)amino group, di(ethoxybutoxybutyl)amino group,di(propoxybutoxybutyl)amino group, di(butoxybutoxybutyl)amino group,di[(4-ethylcyclohexyloxy)ethoxyethyl]amino group,di[(2-ethyl-1-hexyloxy)ethoxypropyl]amino group anddi{[4-(3,5,5-trimethylhexyloxy)butoxy]ethyl}amino group;

alkoxycarbonyl-substituted dialkylamino groups of 3 to 10 in carbonnumber, such as di(methoxycarbonylmethyl)amino group,di(ethoxycarbonylmethyl)amino group, di(n-propoxycarbonylmethyl)aminogroup, di(isopropoxycarbonylmethyl)amino group anddi[(4′-ethylcyclohexyloxy)carbonylmethyl]amino group;

acyl-substituted dialkylamino groups of 3 to 10 in carbon number, suchas di(acetylmethyl)amino group, di(ethylcarbonylmethyl)amino group,di(octylcarbonylmethyl)amino group and di(phenacyl)amino group;

acylamino-substituted dialkylamino groups of 3 to 10 in carbon number,such as di(acetyloxymethyl)amino group, di(acetyloxyethyl)amino group,di(acetyloxyhexyl)amino group and di(butanoyloxycyclohexyl)amino group;

dialkylamino-substituted dialkylamino groups of 2 to 10 in carbonnumber, such as di(methylaminomethyl)amino group,di(2-methylaminoethyl)amino group, di(2-(2-methylaminoethoxy)ethyl)aminogroup, di(4-methylaminobutyl)amino group,di(1-methylaminopropane-2-yl)amino group, di(3-methylaminopropyl)aminogroup, di(2-methylamino-2-methylpropyl)amino group,di(2-ethylaminoethyl)amino group, di(2-(2-ethylaminoethoxy)ethyl)aminogroup, di(3-ethylaminopropyl)amino group, di(1-ethylaminopropyl)aminogroup, di(2-isopropylaminoethyl)amino group,di(2-(n-butylamino)ethyl)amino group, di(3-(n-hexylamino)propyl)aminogroup and di(4-(cyclohexylamino)butyl)amino group;

alkylaminodialkylamino-substituted dialkylamino groups of 3 to 10 incarbon number, such as di(methylaminomethoxymethyl)amino group,di(methylaminoethoxyethyl)amino group, di(methylaminoethoxypropyl)aminogroup, di(ethylaminoethoxypropyl)amino group anddi[4-(2′-isobutylaminopropoxy)butyl]amino group;

didialkylamino-substituted dialkylamino groups of 3 to 15 in carbonnumber, such as di(dimethylaminomethyl)amino group,di(2-dimethylaminoethyl)amino group,di[2-(2-dimethylaminoethoxy)ethyl]amino group,di(4-dimethylaminobutyl)amino group,di(1-dimethylaminopropane-2-yl)amino group,di(3-dimethylaminopropyl)amino group,di(2-dimethylamino-2-methylpropyl)amino group,di(2-diethylaminoethyl)amino group,di[2-(2-diethylaminoethoxy)ethyl]amino group,di(3-diethylaminopropyl)amino group, di(1-diethylaminopropyl)aminogroup, di(2-diisopropylaminoethyl)amino group,di[2-(di-n-butylamino)ethyl]amino group, di(2-piperidylethyl)amino groupand di[3-(di-n-hexylamino)propyl]amino group;

dialkylaminodialkylamino-substituted dialkylamino groups of 4 to 15 incarbon number, such as di(dimethylaminomethoxymethyl)amino group,di(dimethylaminoethoxyethyl)amino group,di(dimethylaminoethoxypropyl)amino group,di(diethylaminoethoxypropyl)amino group anddi(4-(2′-diisobutylaminopropoxy)butyl)amino group;

dialkylamino-substituted dialkylamino groups of 2 to 15 in carbonnumber, such as methylthiomethyl)amino group, di(2-methylthioethyl)aminogroup, di(2-ethylthioethyl)amino group, di(2-n-propylthioethyl)aminogroup, di(2-isoporpylthioethyl)amino group, di(2-n-butylthioethyl)aminogroup, di(2-isobutylthioethyl)amino group and[(3,5,5-trimethylhexylthio)hexyl]amino group;

and the like; more preferably: dialkylamino groups of 1 to 10 in carbonnumber, such as dimethylamino group, diethylamino group,di(n-propyl)amino group, di(iso-propyl)amino group, di(n-butyl)aminogroup, di(iso-butyl)amino group, di(sec-butyl)amino group,di(t-butyl)amino group, di(n-pentyl)amino group, di(iso-pentyl)aminogroup, di(neopentyl)amino group, di(2-methylbutyl)amino group,di(n-hexyl)amino group, di(n-heptyl) amino group, di(n-octyl)aminogroup, di(2-ethylhexyl)amino group, di(3,5,5-trimethylhexyl)amino group,di(decalyl)amino group, di(methoxyethyl)amino group,di(ethoxyethyl)amino group, di(methoxyethoxyethyl)amino group,di(ethoxyethoxyethyl)amino group and di(n-decyl)amino group;

diaralkylamino groups of 14 to 20 in carbon number, such asdibenzylamino group, diphenethylamino group, bis(4-ethylbenzyl)aminogroup and bis(4-isopropylbenzyl)amino group;

diarylamino groups of 12 to 14 in carbon number, such as diphenylaminogroup, ditolylamino group, dixylylamino group, N-phenyl-N-tolylaminogroup, N-phenyl-N-xylylamino group and dimesitylamino group;

dialkenylamino groups of 4 to 12 in carbon number, such as divinylaminogroup, diallylamino group, dibutenylamino group, dipentenylamino group,dihexenylamino group, bis(cyclopentadienyl)amino group andN-vinyl-N-allylamino group;

diacylamino groups of 2 to 30 in carbon number, such as diformylaminogroup, di(methylcarbonyl)amino group, di(ethylcarbonyl)amino group,di(n-propylcarbonyl)amino group, di(iso-propylcarbonyl)amino group,di(n-butylcarbonyl)amino group, di(iso-butylcarbonyl)amino group,di(sec-butylcarbonyl)amino group, di(t-butylcarbonyl)amino group,di(n-pentylcarbonyl)amino group, di(iso-pentylcarbonyl)amino group,di(neopentylcarbonyl)amino group, di(2-methylbutylcarbonyl)amino group,di(benzoyl)amino group, di(methylbenzoyl)amino group, di (ethylbenzoyl)amino group, di(tolylcarbonyl) amino group, di(propylbenzoyl)aminogroup, di(4-t-butylbenzoyl)amino group, di(nitrobenzylcarbonyl)aminogroup, di(3-butoxy-2-naphthoyl)amino group, di(cinnamoyl)amino group andsuccinic nitrogen atom;

and disubstituted amino groups of 3 to 24 in carbon number containingsubstituents selected from substituted or unsubstituted alkyl groups,aralkyl groups, aryl groups and alkenyl groups, such asN-phenyl-N-allylamino group, N-(2-acetyloxyethyl)-N-ethylamino group,N-tolyl-N-methylamino group, N-vinyl-N-methylamino group,N-benzyl-N-allylamino group, N-methyl-ferrocenylamino group,N-ethyl-cobaltcenylamino group, N-butyl-nickelocenylamino group,N-hexyl-octamethylferrocenylamino group,N-methyl-octamethylcobaltcenylamino group,N-methyl-octamethylnickelocenylamino group.

As specific examples of the methine groups which may have substituents,shown by X¹ to X⁸ in the frameworks of the azaannulene rings of GeneralFormula (1), are methine groups respectively shown in General Formulae(5) to (12)

[In the formulae, G¹ to G⁸ each represent hydrogen atoms or arbitrarysubstituents.] As favorable examples of the substituents, hydrogen atom;halogen atoms such as fluorine atom, chlorine atom, bromine atom andiodine atom; cyano group; substituted or unsubstituted alkyl groups;substituted or unsubstituted aralkyl groups; substituted orunsubstituted aryl group; substituted or unsubstituted alkenyl group;acyloxy groups; etc. can be mentioned.

Also, regarding G¹ to G⁸ of General Formulae (5) to (12), which aresubstituents in R¹ to R¹⁶ and the methine groups of General Formula (1),those substituents may bond to each other through connecting radicalsbetween them; specifically, the formation of rings by aliphaticcondensation or aromatic condensation, the formation of heterocyclicrings whose connecting radicals contain hetero atoms or hetero atomssuch as metal complex residues, or the like can be mentioned.

Connecting radicals used when R¹ to R¹⁶ and G¹ to G⁸ each bond toadjacent substituents through the connecting radicals to form rings, aregroupes made of selecting and combining accordingly from hetero atomssuch as oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, metalatom and metalloid atom, and carbon atom. As preferable examples of theconnecting radicals, —O—; —S—; —C(═O)—; methylene groups, methinegroups, ethynylene groups, phenylene groups, amino groups, imino groups,metal atoms and metalloid atoms which may be substituted; or the likecan be mentioned, and desired rings can be obtained by suitablycombining those groupes to make connecting chains. As rings formed byconnecting chains, chain-like, planar or three-dimensional rings can bementioned. As favorable examples of connecting chains when rings areformed by connection and as rings obtained: alicyclic condensed ringsmade of aliphatic chains, such as —CH₂—CH₂—CH₂—CH₂—,—CH₂(NO₂)—CH₂—CH₂—CH₂—, —CH(CH₃)—CH₂—CH₂—CH₂— and —CH(Cl)—CH₂—CH₂—;

aromatic condensed rings made of aliphatic chains, such as—CH═CH—CH═CH—, —C(NO₂)═CH—CH═CH—, —C(CH₃)═CH—CH═CH—, —C(CH₃)═CH—CH═CH—,—C(CH₃)═CH—CH═C(CH₃)—, —C(OCH₃)═CH—CH═C(OCH₃)—, —C(OCH₂CH₂CH(CH₃)—(OCH₃))═C(Cl)—C(Cl)═C(OCH₂CH₂CH(CH₃)— (OCH₃))—,—C(OCH₂CH₂CH(CH₃)₂)═C(Cl)—C(Cl)═C(OCH₂CH₂CH(CH₃)₂)—,—CH═C(CH₃)—C(CH₃)═CH—, —C(Cl)═CH—CH═CH—, —C{OCH[CH(CH₃)₂]₂}═CH—CH═CH—,C{OCH[CH(CH₃)₂]₂}═C(Br)—CH═CH—, —C{OCH[CH(CH₃)₂]₂}═CH—C(Br)═CH—, —C{OCH[CH(CH₃)₂]₂}═CH—CH═C(Br)—, —C(C₂H₅)═CH—CH═CH—, —C(C₂H₅)═CH—CH═C(C₂H₅)—,—CH═C(C₂H₅)—C(C₂H₅)═CH— and —C(Cl)═CH—CH═CH—;

heterocyclic rings made of aliphatic chains, containing hetero atoms incarbon-carbon atom chains, such as —O—CH₂—CH₂—O—, —O—CH(CH₃)—CH(CH₃)—O—,—COO—CH₂—CH₂—, —COO—CH₂—, —CONH—CH₂—CH₂—, —CONH—CH₂—,—CON(CH₃)—CH₂—CH₂—, —CON(CH₃)—CH₂—, —S—CH₂—CH₂—S—,—S—CH(CH₃)—CH(CH₃)—S—, —N═CH—CH═N— and —CH═NN═CH—; or heterocyclicgroups and the like, such as the following metal complex residues:

(M′ represents Fe, Ru, Co, Ni, Os or M″R′₂ (M″ represents Ti, Zr, Hf,Nb, Mo, V, and R′ represents CO, F, Cl, Br, I, or alkyl groups, alkoxygroups, aryl groups, aryloxy groups, aralkyl groups and aralkyloxygroups of 1 to 10 in carbon number containing substituents similar tothe above-mentioned R¹ to R¹⁶.).)

As specific examples of substituted or unsubstituted sulfur atomscontained between carbon-carbon atoms in substituted or unsubstitutedhydrocarbon radicals and/or in hydrocarbon-substituted substitutedhydroxyl groups, substituted mercapto groups and substituted aminogroups indicated by R¹ to R¹⁶ of General Formula (1), and in G¹ to G⁸which are substituents of methane groupes of General Formulae (5) to(12), unsubstituted sulfur atoms such as thia group; oxygen-substitutedsulfur atoms such as sulfonyl group and sulfinyl group; and the like canbe mentioned.

As specific examples of substituted or unsubstituted sulfur atomscontained between carbon-carbon atoms in substituted or unsubstitutedhydrocarbon radicals and/or in hydrocarbon-substituted substitutedhydroxyl groups, substituted mercapto groups and substituted aminogroups indicated in R¹ to R¹⁶ of General Formula (1), and in G¹ to G⁸which are substituents of methane groupes of General Formulae (5) to(12), unsubstituted nitrogen atoms such as —N═; and substituted nitrogenatoms such as hydrogen or the aforementioned hydrocarbon substitutedimino group can be mentioned.

As bivalent to tetravalent metal atoms or trivalent to tetravalentmetalloid atoms represented by M, the metal atoms and metalloid atoms inGroups IIA to VIIA, Group VIII and Groups IB to VIIB on the periodictable can be mentioned.

As specific examples of bivalent metal atoms which may have ligands,bivalent unsubstituted metal atoms such as Cu, Zn, Fe, Co, Ni, Ru, Rh,Pd, Pt, Mn, Sn, Mg, Pb, Hg, Cd, Ba, Ti, Be, Ca, Re, Os, or the like, orbivalent metal atoms with which substituted or unsubstitutedheterocyclic compounds such as five-membered ring nitrogen-containingaromatic compounds, six-membered ring nitrogen-containing aromaticcompounds and condensed ring nitrogen-containing compounds, carbonmonoxide, alcohols, or the like coordinate as ligands can be mentioned.

As examples of the substituted or unsubstituted five-membered ringnitrogen-containing aromatic compounds which coorinate with the bivalentmetal atoms, pyrrole, methylpyrrole, dimethylpyrrole, pyrazole,N-methylpyrazole, 3,5-dimethylpyrazole, imidazole, N-methylimidazole,methylimidazole, 1,2-dimethylimidazole, oxazole, thiazole,4-methylthiazole, 2,4-dimethylthiazole, 1,2,3-oxadiazole, triazole,1,3,4-thiadiazole, 2,5-dimethyl-1,3,4-thiadiazole and the like can bementioned.

As examples of the substituted or unsubstituted six-membered ringnitrogen-containing aromatic compounds which coorinate with the bivalentmetal atoms, pyridine, 2-methylpyridine, 3-methylpyridine,4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine,2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine,3,5-dimethylpyridine, 2-chloropyridine, 3-chloropyridine,2-methoxypyridine, pyridazine, 3-methylpyridazine, pyrimidine,4-methylpyrimidine, 2-chloropyrimidine, pyrazine, 2-methylpyrazine,2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2-methoxypyrazine,s-triazine and the like can be mentioned.

As examples of the substituted or unsubstituted condensed ringnitrogen-containing compounds which coorinate with the bivalent metalatoms, indole, N-methylindole, 2-methylindole, 3-methylindole,5-methylindole, 1,2-dimethylindole, 2,3-dimethylindole, 4-chloroindole,5-chloroindole, 6-chloroindole, 4-methoxyindole, 5-methoxyindole,6-methoxyindole, benzimidazole, 2-methylbenzimidazole,5-methylbenzimidazole, 5,6-dimethylbenzimidazole, 5-chlorobenzimidazole,benzothiazole, 2-methylbenzothiazole, 2,5-dimethylbenzothiazole,2-chlorobenzothiazole, purine, quinoline, 2-methylquinoline,3-methylquinoline, 4-methylquinoline, 6-methylquinoline,7-methylquinoline, 8-methylquinoline, 2,4-dimethylquinoline,2,6-dimethylquinoline, 2-chloroquinoline, 6-chloroquinoline,8-chloroquinoline, 6-methoxyquinoline, isoquinoline, 1-methylquinoline,quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, carbazole,N-methylcarbazole, acridine, 9-methylacridine, phenothiazine and thelike can be mentioned.

As favorable specific examples of the bivalent metal atoms,unsubstituted or two-coordinate bivalent metal atoms such as Cu, Ni, Co,Rh, Zn, Fe, Cu(pyridine)₂, Zn(pyridine)₂, Co (pyridine)₂,Fe(N-methylimidazole), Co(N-methylimidazole) or the like can bementioned.

When n is 0, M in General Formula (1) represents a trivalent ortetravalent metal or metalloid atom having a substituent.

As trivalent metal or metalloid atoms having substituents, representedby M, trivalent metal atoms or metalloid atoms of such as Sc, Ti, V, Cr,Mn, Mo, Ag, U, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh, La, Ta, Ir, Au, In, Tl,Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, As, Sb,or the like, in which as substituents selected and bonded are in theabove described R₁ to R₁₆ halogen atoms, hydroxyl groups; and alkylgroups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups,heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthiogroups and amino groups which may have substituents, similarly to theaforementioned halogen atoms, hydroxyl groups; and alkyl groups, arylgroups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxygroups, alkylthio groups, arylthio groups, heteroarylthio groups andamino groups which may have substituents, or alkyl- and aryl-substitutedsilyloxy groups; or in which as substituents selected and bonded arehalogen atoms as described above, alkyl groupes, aryl groupes,heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups,alkylthio groups, arylthio groups, heteroarylthio groups and aminogroups, wherein as ligands, heterocyclic compounds such as substitutedor unsubstituted five-membered ring nitrogen-containing aromaticcompounds, six-membered ring nitrogen-containing aromatic compounds andcondensed ring nitrogen-containing compounds, carbon monoxide, alcohols,etc. are coordinated can be mentioned.

As examples of the alkyl- and aryl-substituted silyloxy groups,trialkylsilyloxy groups such as trimethylsilyloxy group andtriethylsilyloxy group, triarylsilyloxy groups such as triphenylsilyloxygroup, alkylarylsilyloxy groups such as dimethylphenylsilyloxy group,and the like can be mentioned.

As favorable specific examples of the trivalent metal atoms,1-substituted trivalent metal atoms such as Al—F, Al—Cl, Al—Br, Al—I,Ga—F, Ga—Cl, Ga—Br, Ga—I, In—F, In—Cl, In—Br, In—I, Ti—F, Ti—Cl, Ti—Br,Ti—I, Al—C₆H₅, Al—C₆H₄(CH₃), In—C₆H₅, In—C₆H₄(CH₃), Mn(OH), Mn(OC₆H₅)Mn[OSi(CH₃)₃], Fe—Cl, Fe—Cl(bis(N-methylimidazole)), Fe-(imidazolyloxy)and Ru—Cl or the like can be mentioned.

As favorable specific examples of the trivalent metalloid atoms,1-substituted trivalent metalloid atoms such as B—F, B—OCH₃, B—C₆H₅,BC₆H₄(CH₃), B(OH), B(OC₆H₅) and B[OSi(CH₃)₃] can be mentioned.

As tetravalent metal or metalloid atoms having substituents representedby M, tetravalent metal or metalloid atoms of Ti, Cr, Sn, Zr, Ge, Mn, Sior the like can be mentioned, in which as substituents selected andbonded are among halogen atoms, hydroxyl groups; and alkyl groups, arylgroups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxygroups, alkylthio groups, arylthio groups, heteroarylthio groups andamino groups which may have substituents similar to the above shown R¹to R¹⁶ of halogen atoms, hydroxyl groups; and alkyl groups, aryl groups,heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups,alkylthio groups, arylthio groups, heteroarylthio groups and aminogroups which may have substituents, or selected and bonded from alkyl-and aryl-substituted silyloxy groups or oxygen atoms, whereinheterocyclic compounds such as substituted or unsubstitutedfive-membered ring nitrogen-containing aromatic compounds, six-memberedring nitrogen-containing aromatic compounds and condensed ringnitrogen-containing compounds, carbon monoxide, alcohols or the like maybe coordinated as ligands.

As favorable specific examples of the tetravalent metal atoms,2-substituted tetravalent metal atoms such as TiF₂, TiCl₂, TiBr₂, TiI₂,CrF₂, CrCl₂, CrBr₂, CrI₂, SnF₂, SnCl₂, SnBr₂, SnI₂, ZrF₂, ZrCl₂, ZrBr₂,ZrI₂, GeF₂, GeCl₂, GeBr₂, GeI₂, MnF₂, MnCl₂, MnBr₂, MnI₂, Ti(OH)₂,Cr(OH)₂, Sn(OH)₂, Zr(OH)₂, Ge(OH)₂, Mn(OH)₂, TiA₂, CrA₂, 5 nA₂, ZrA₂,GeA₂, MnA₂, Ti(OA)₂, Cr(OA)₂, Sn(OA)₂, Zr(OA)₂, Ge(OA)₂, Mn(OA)₂,Ti(SA)₂, Cr(SA)₂, Sn(SA)₂, Zr(SA)₂, Ge(SA)₂, Mn(SA)₂, Ti(NHA)₂,Cr(NHA)₂, Sn(NHA)₂, Zr(NHA)₂, Ge(NHA)₂, Mn(NHA)₂, Ti(NA₂)₂, Cr(NA₂)₂,Sn(NA₂)₂, Zr(NA₂)₂, Ge(NA₂)₂ and Mn(NA₂)₂ [A represents substituted orunsubstituted alkyl groups, aryl groups and heteroaryl groups similar tothe above-mentioned alkyl groups, aryl groups and heteroaryl groupsrepresented by R¹ to R¹⁶.] can be mentioned.

As favorable specific examples of the tetravalent metalloid atoms,2-substituted tetravalent metalloid atoms such as SiF₂, SiCl₂, SiBr₂,SiI₂, Si(OH)₂, SiA₂, Si(OA)₂, Si(SA)₂, Si(NHA)₂ and Si(NA₂)₂ [A meansthe aforementioned A.] can be mentioned.

As specific examples of oxo metal atoms, which are tetravalent metalatoms with oxgen atoms bonded, VO, MnO, TiO and the like can bementioned.

As M, preferably Cu, Ni, Co, Rh, Zn, Fe, MnCl, CoCl, FeCl,Fe(N-methylimidazolyloxy), Fe—Cl(bis(N-methylimidazole)), Cu(pyridine)₂,Zn(pyridine)₂, Co(pyridine)₂, Fe(N-methylimidazole),Co(N-methylimidazole)₂, VO, TiO, TiA₂, SiA₂, 5 nA₂, RuA₂, RhA₂, GeA₂,Si(OA)₂, Sn(OA)₂, Ge(OA)₂, Si(SA)₂, Sn(SA)₂ and Ge(SA)₂ [A means theaforementioned A.] can be mentioned.

Further, when n is 1, M represents a trivalent metal atom and onehydrogen atom, or a tetravalent metal atom.

As regards M, each of the atoms in Groups IIIA to VIIA, Group VIII andGroups IB to VIIB on the periodic table can be used with one hydrogenatom. As preferable examples, trivalent unsubstituted metal atoms suchas Sc, Ti, V, Cr, Mn, Mo, Ag, U, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh, La, Ta,Ir, Au, In, Tl, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb and Lu can be mentioned. More preferably, Lu, Ce, Sm, Ru, Eu, Y, Rhand the like can be mentioned.

As the tetravalent metal atoms represented by M, the metal atoms inGroups IIIA to VIIA, Group VIII and Groups IB to VIIB on the periodictable can be mentioned. As preferable examples, trivalent unsubstitutedmetal atoms such as Ti, V, Cr, Mn, Mo, Zr, Nb, Ru, Rh, Ta, Ir, Pb, Ce,Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like can bementioned. More preferably, Zr, Lu, Ce, Ru, Rh and the like can bementioned.

Also, in the present invention, compounds shown by General Formula (2)can be mentioned as favorable examples shown by General Formula (1).

[In the formula, R¹⁷ to R²⁴ each show a hydrogen atom, a halogen atom, anitro group, a cyano group, a substituted or unsubstituted hydrocarbonradical, a substituted or unsubstituted hydroxy group, a substituted orunsubstituted mercapto group, or a substituted or unsubstituted aminogroup individually; substituents in R¹⁷ to R²⁴ may bond to substituentson a tetraazaporphyrin ring to form aliphatic rings through a connectingradicals; and there may be contained oxygen atoms, substituted orunsubstituted sulfur atoms and substituted or unsubstituted nitrogenatoms between carbon atoms in substituted or unsubstituted hydrocarbonradicals and/or in hydrocarbon-substituted substituted hydroxyl groups,substituted mercapto groups and substituted amino groups. M¹ representsa bivalent metal atom which may have ligands, or a trivalent ortetravalent metal or metalloid atom which has a substituent and/orligands.]

As regards compounds shown by General Formula (2) of the presentinvention, a hydrogen atom; a halogen atom such as a fluorine atom, achlorine atom, a bromine atom, an iodine atom, etc.; a nitro group; acyano group; or the like can be mentioned as a specific example of eachof R¹⁷ to R²⁴.

As examples of substituted or unsubstituted hydroxy groups, substitutedor unsubstituted mercapto groups and substituted or unsubstituted aminogroups used for R¹⁷ to R²⁴, substituted or unsubstituted hydroxylgroups, substituted or unsubstituted mercapto groups and substituted orunsubstituted amino groups similar to the aforementioned R¹ to R¹⁶ canbe mentioned.

As the connecting radicals used when R¹⁷ to R²⁴ bond to form aliphaticrings through connecting radicals, connecting radicals similar to theabove-described R¹ to R¹⁶ can be mentioned.

As examples of the bivalent metal atoms which may have ligands, ortrivalent or tetravalent metal or metalloid atoms which havesubstituents and/or ligands, used for M¹, metal atoms similar to theabove-mentioned M can be mentioned.

Also, in the present invention, compounds shown by General Formula (3)can be mentioned as favorable examples shown by General Formula (1).

[In the formula, R²⁵ to R⁴⁰ each show a hydrogen atom, a halogen atom, anitro group, a cyano group, a substituted or unsubstituted hydrocarbonradical, a substituted or unsubstituted hydroxy group, a substituted orunsubstituted mercapto group, or a substituted or unsubstituted aminogroup individually; X⁹ to X¹⁶ each show a nitrogen atom, or asubstituted or unsubstituted methine group individually; substituents inR²⁵ to R⁴⁰ and in methine groups may each bond to form aliphatic ringsthrough connecting radicals; and there may be contained oxygen atoms,substituted or unsubstituted sulfur atoms and substituted orunsubstituted nitrogen atoms between carbon atoms in substituted orunsubstituted hydrocarbon radicals and/or in hydrocarbon-substitutedsubstituted hydroxy groups, substituted mercapto groups and substitutedamino groups. Also, n represents 0 or 1; when n is 0, M² represents abivalent metal atom which may have ligands, or a trivalent ortetravalent metal or metalloid atom which has substituents and/orligands, and when n is 1, M² represents a trivalent metal atom and onehydrogen atom, or a tetravalent metal atom.]

As regards compounds shown by General Formula (3) of the presentinvention, a hydrogen atom; a halogen atom such as a fluorine atom, achlorine atom, a bromine atom, an iodine atom, etc.; a nitro group; acyano group; or the like can be mentioned as a specific example of R²⁵to R⁴⁰ each.

As examples of substituted or unsubstituted hydroxy groups, substitutedor unsubstituted mercapto groups and substituted or unsubstituted aminogroups used for R²⁵ to R⁴⁰, substituted or unsubstituted hydroxylgroups, substituted or unsubstituted mercapto groups and substituted orunsubstituted amino groups similar to the above-mentioned R¹ to R¹⁶ canbe mentioned.

As the connecting radicals used when R²⁵ to R⁴⁰ each bond to formaliphatic rings through connecting radical, connecting radicals similarto the above-mentioned R¹ to R¹⁶ can be mentioned.

As regards the metal or metalloid atoms used for M², when n is 0, metalatoms similar to the above-mentioned M can be mentioned as examples ofthe bivalent metal atoms which may have ligands, or trivalent ortetravalent metal or metalloid atoms which have substituents and/orligands. Also, regarding M², when n is 1, metal atoms similar to theabove-mentioned M can be mentioned as an example of a trivalent metalatom and one hydrogen atom, or a tetravalent metal atom.

Also, in the present invention, compounds shown by General Formula (4)can be mentioned as favorable examples shown by General Formula (1).

[In the formula, R⁴¹ to R⁷² each show a hydrogen atom, a halogen atom, anitro group, a cyano group, a substituted or unsubstituted hydrocarbonradical, a substituted or unsubstituted hydroxy group, a substituted orunsubstituted mercapto group, or a substituted or unsubstituted aminogroup individually; substituents in R⁴¹ to R⁷² may each bond to asubstituent on a phthalocyanine ring through connecting radicals; andthere may be contained oxygen atoms, substituted or unsubstituted sulfuratoms and substituted or unsubstituted nitrogen atoms between carbonatoms in substituted or unsubstituted hydrocarbon radicals and/or inhydrocarbon-substituted substituted hydroxy groups, substituted mercaptogroups and substituted amino groups. n represents 0 or 1; when n is 0,M³ represents a bivalent metal atom which may have ligands, or atrivalent or tetravalent metal or metalloid atom which has asubstituent, and when n is 1, M³ represents a trivalent metal atom andone hydrogen atom, or a tetravalent metal atom.]

As regards compounds shown by General Formula (4) of the presentinvention, a hydrogen atom; a halogen atom such as a fluorine atom, achlorine atom, a bromine atom, an iodine atom, etc.; a nitro group; acyano group; or the like can be mentioned as a specific example of eachof R⁴¹ to R⁷².

As examples of substituted or unsubstituted hydroxy groups, substitutedor unsubstituted mercapto groups and substituted or unsubstituted aminogroups used for R⁴¹ to R⁷², substituted or unsubstituted hydroxylgroups, substituted or unsubstituted mercapto groups and substituted orunsubstituted amino groups similar to the above-mentioned R¹ to R¹⁶ canbe mentioned.

As the connecting radicals used when R⁴¹ to R⁷² bond to form ringsthrough connecting radicals, connecting radicals similar to theabove-mentioned R¹ to R¹⁶ can be mentioned.

As regards the metal or metalloid atoms used for M³, when n is 0, metalatoms similar to the above-mentioned M can be mentioned as examples ofthe bivalent metal atoms which may have ligands, or trivalent ortetravalent metal or metalloid atoms which have substituents and/orligands. Also, regarding M³, when n is 1, metal atoms similar to theabove-mentioned M can be mentioned as an example of a trivalent metalatom and one hydrogen atom, or a tetravalent metal atom.

Among the azaannulene compounds described in the present invention, thecompounds of General Formula (1) can be favorably used for recording,reproducing and erasure by a blue-violet nitride-based semiconductorlaser of 350 to 450 nm in the oscillation wavelength band, by the redsemiconductor laser of 600 to 650 nm in wavelength used for the DVD-R,and by the near-infrared semiconductor laser of 750 to 850 nm inwavelength used for the CD-R. Hereupon, the compounds of General Formula(3) can be more favorably used for recording, reproduction and erasureby the red semiconductor laser 600 to 650 nm in wavelength used for theDVD-R, and the compounds of General Formula (4) can be more favorablyused for recording, reproduction and erasure by the near-infraredsemiconductor laser of 750 to 850 nm in wavelength used for the CD-R.Particularly, the compounds of General Formula (2) is favorably used forrecording, reproduction and erasure both in the oscillation wavelengthband of a blue-violet nitride-based semiconductor laser of 350 to 450nm, and of the red semiconductor laser wavelength of 600 to 650 nm usedfor the DVD-R.

As regards the compounds shown by General Formula (1) used for thepresent invention, the ones whose n is 0 are not limited; however, forexample, tetraazaporphyrin (otherwise called porphyrazine) compoundswhose X¹ to X⁴ are all nitrogen are produced according to the methodsdescribed in J. Gen. Chem. USSR vol. 47, ppl 1954-1958 (1977) and thelike, for example. Typically, those compounds can be produced by thefollowing reactions.

Specifically, at least one kind of the following compounds shown byGeneral Formulae (13) to (16) is used and heated to react with organicmetallic salt such as acetylacetonato salt, acetate, trifluoroacetate,etc. of a bivalent or tetravalent metal atom or a hydrate thereof, orwith inorganic metallic salt such as halide, sulfate, nitrate,perchlorate, chlorate, hypochlorite, etc. of a metal atom, or a hydratethereof, under the existence of a base such as1,8-diazabicyclo[5.4.0]-7-undecene depending on a case, in a solvent ofalcohol such as pentanol, hexanol, etc. or of aromatic solvent such asbenzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene,1,2,4-trichlorobenzene, etc, so that Phthalocyanine compounds of GeneralFormula (1) whose n is 0, and four of whose X¹ to X⁴ are nitrogen; ortetraazaporphyrin compounds of General Formula (2) can be obtained.

[In the formulae, each of R⁷³ to R⁸⁰ means the same as R¹ to R⁸ ofGeneral Formula (1) respectively.]

Also, metal-free tetraazaporphyrin compounds can be obtained by makingthe tetraazaporphyrin compounds of General Formula (2) react with acidsuch as an organic acid of trifluoroacetic acid or the like in a solventsuch as chloroform, etc., or by making a Grignard reagent such asmethylmagnesiumbromide react with the tetraazaporphyrin compounds ofGeneral Formula (2), and treating them with an acid such as hydrochloricacid or sulfuric acid afterward.

Also, monoazaporphyrin-based compounds whose n is 0, and one of whose X¹to X⁴ is nitrogen are not particularly restricted, and can be producedaccording to the methods described in Bull. Chem. Soc. Jpn., 61,3539-3547(1988); Inorg. Chem., 32, 291-296(1993); Tetrahedron Lett.,36(10), 1567-1570(1995); Liebigs Ann. Chem., 399-359(1977); InorganicaChimica Acta, 203, 107-114(1993); and the like, for example. Typically,the compounds can be produced by the following methods, for example.

That is, the condensed body of Formula (20) or hydrobromate thereof isobtained by making dipyromethane compounds of General Formula (17) andpyrrole compounds of General Formulae (18) to (19) react, under theexistence of hydrobromic acid, in solvent such as halogenated solventsuch as methylene chloride, a alcohol-based solvent such as ethanol, orthe like.

[In the formulae, R⁸¹, R⁸², R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁹ and R⁹⁰ each meanthe same as R¹ to R⁸ of Formula (1) respectively, R⁸³, R⁸⁸ and R⁹ eachmean the same as the substituents in the methine groups, which are X¹ toX⁴ of Formula (1), respectively, and r represents a hydrogen atom orcarboxyl group.]

[In the formula, R⁹², R⁹³, R⁹⁵, R⁹⁶, R⁹⁸, R⁹⁹, R¹⁰¹ and R¹⁰¹ each meanthe same as R¹ to R⁸ of Formula (1) respectively, and R⁹⁴, R⁹⁷ and R¹⁰⁰each mean the same as the substituents in the methine groups, which areX¹ to X⁴ of Formula (1) respectively.]

Next, dihalogenated compounds of General Formula (21) is obtained byhalogenating the condensed body shown by General Formula (20) with ahalogenating agent such as bromine, iodine, N-bromosuccinimide,N-iodosuccinimide, etc. in solvent such as an organic acid such asacetic acid, methylene chloride, trifluoroacetic acid, etc., ahalogenated solvent, or an alcohol-based solvent such as ethanol.

[In the formula, R⁹² to R¹⁰² represent the same groups as R⁹² to R¹⁰² inFormula (20), respectively, and a represents a halogen atom.]

Next, monoazaporphyrin-based compounds whose n is 0, and one of whose X¹to X⁴ is nitrogen in General Formula (1) can be obtained by making thedihalogenated compounds react with an azide salt such as sodium azide;with or without a metallic or metalloidal compound such as an inorganicsalt of sulfate, nitrate, halogenated salt, etc. of metal or metalloid,or an organic metallic salt of acetate, acetylacetonato salt, etc., acoordinating compound such as pyridine, etc. capable of coordinatingwith metal, an ionic compound such as sodium chloride, sodiumfluoroborate, etc., whose anions are capable of coordinating with metal,an oxidizing agent such as air, etc., a neutralizer such asN-ethyldiisopropylamine, triethanolamine, etc., or a phase-transfercatalyst such as benzo-18-crown-6-ether, etc. existed; in analcohol-based solvent such as methanol or ethanol, a halogenated solventsuch as methylene chloride, or an amide-based solvent such asN,N-dimethylformamide.

Also, metal-free monoazaporphyrin compounds can be obtained by makingmonoazaporphyrin compounds which have been made metal complexes reactwith an acid such as an organic acid of trifluoroacetic acid or the likein a solvent such as chloroform, etc., or by making a Grignard reagentsuch as methylmagnesiumbromide react therewith, and treating them withan acid such as hydrochloric acid or sulfuric acid afterward.

Also, diazaporphyrin-based compounds whose n is 0, and two of whose X¹to X⁴ are nitrogen are not particularly restricted, and they can beproduced according to the methods described in J. Chem. Soc. (C),22-29(1996); J. Biochem., 121, 654-660(1997); Z. Physiol. Chem, 214,145(1933); Die Chemie des Pyrrols, Band II, Halfte 2, pp. 411-414,Akademische Verlagesellschuft, Leipzig(1940); and the like, for example.Typically, they can be produced by the following reaction includingthree stages.

To begin with, at the first stage, dipyromethene compounds shown byGeneral Formulae (24) and (25) are obtained by halogenatingdipyromethane compounds shown by General Formulae (22) and (23) with ahalogenating agent such as bromine, iodine, N-bromosuccinimide,N-iodosuccinimide, etc. in a carboxylic acid-based solvent such asacetic acid, or a halogenated hydrocarbon-based solvent such asmethylene chloride.

[In the formulae, R¹⁰³, R¹⁰⁴, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸, R¹⁰⁹, R¹¹¹ and R¹¹² meanthe same as R¹ to R⁸ of Formula (1) respectively, R¹¹³ and R¹¹⁸ mean thesame as the substituents in the methine groups of Formula (1)respectively, and r represents a hydrogen atom or carboxyl group.]

[In the formulae, R¹¹³ to R¹²² represent the same groups as R¹⁰³ to R¹¹²of Formulae (22) and (23), and a represents a halogen atom.]

Then, at the second stage, dipyromethene metal complexes shown byGeneral Formula (26) are obtained by making the dipyromethene compoundsof General Formulae (24) and (25) react, using an inorganic salt ofsulfate, nitrate, halogenated salt, etc. of metal or metalloid, or metalor metalloid of an organic metallic salt such as acetate,acetylacetonato salt, etc., with or without an oxidizing agent such asair existed, in organic solvents such as an alcohol-based solvent suchas ethanol and/or an amide solvent such as dimethylformamide.

[In the formula, R¹¹³ to R¹²² and a each represent the same groups asR¹¹³ to R¹²² and a of Formulae (24) and (25), and M⁴ means the same as Mof Formula (1).]

Subsequently, at the third stage, diazaporphyrin compounds whose n is 0,and two of whose X¹ to X⁴ are nitrogen in Formula (1) can be obtained bymaking the dipyromethene metal complexes (26) react with an azide saltsuch as sodium azide in organic solvents of an alcohol-based solventsuch as ethanol and/or an amide solvent such as dimethylformamide.

Hereupon, the above diazaporphyrin compounds can also be obtained bymaking the dipyromethene compounds of General Formulae (24) and (25)obtained at the first stage react with an azide salt such as sodiumazide, using an inorganic salt such as sulfate, nitrate, halogenatedsalt, etc. of metal or metalloid, or an organic metallic salt such asacetate, acetylacetonato salt, etc., or the like, with or without anoxidizing agent such as air existed, in organic solvents of analcohol-based solvent such as ethanol and/or an amide solvent such asdimethylformamide.

Also, metal-free diazaporphyrin compounds can be obtained by makingdiazaporphyrin compounds of metal complexes react with an acid such asan organic acid of trifluoroacetic acid in a solvent such as chloroform,etc., or by making a Grignard reagent such as methylmagnesiumbromidereact with diazaporphyrin compounds of metal complexes, and treatingthem with an acid such as hydrochloric acid or sulfuric acid afterward.

Further, triazaporphyrin-based compounds whose n is 0, and three ofwhose X¹ to X⁴ are nitrogen are not particularly restricted, but theycan be produced according to the methods described in Can. J. Chem. Vol.71, 742-753(1996) and the like, for example. Typically, they can beproduced by the following reactions.

It is also possible to obtain triazaporphyrin compounds whose n is 0,and three of whose X¹ to X⁴ are nitrogen in General Formula (1), byheating compounds shown by the above-described General Formulae (13) to(16) to react with at least one kind of unsaturated ketone compounds ofGeneral Formulae (27) and (28) and with a halogenated metal and/or ametal derivative, with or without a solvent existing.

[In the formulae, R¹²³, R¹²⁴, R¹²⁶ and R¹²⁷ each mean the same as R¹ toR⁸ of Formula (1) respectively, R¹²⁵ and R¹²⁸ mean the same as thesubstituents in the methine groups of Formula (1) respectively, and rrepresents a hydrogen atom or carboxyl group.]

Further, as another method, triazaporphyrinmagnesium complex compoundswhose n is 0, and three of whose X¹ to X⁴ are nitrogen, containingsubstituted methine groups can be obtained by using at least one kind ofcompounds shown by the above-described General Formulae (13) to (16),making a Grignard reagent of General Formula (29) written below workwith a solvent such as ether existed; and further, heating the conpoundwith an amine such as quinoline existed.

[In the formula, R′ means the same as a substituent which substitutes amethine group of Formula (1), and X′ means a halogen atom.]

Also, metal-free triazaporphyrin compounds can be obtained by makingtriazaporphyrin compounds of metal complexes react with an acid such asan organic acid of trifluoroacetic acid in a solvent such as chloroform,etc., or by making a Grignard reagent such as methylmagnesiumbromidereact with triazaporphyrin compounds of metal complexes, and treatingthem with an acid such as hydrochloric acid or sulfuric acid afterward.

Further, porphyrin compounds whose n is 0, and all of whose X¹ to X⁴ aresubstituted or unsubstituted methine groups are not particularlyrestricted, and can be produced according to the methods described in J.Org. Chem. Vol. 58(25), 7245-7257(1993) and the like, for example.Typically, those compounds can be produced by the following reactions.

Metal-free porphyrin compounds whose n is 0, and all of whose X¹ to X⁴are substituted or unsubstituted methine groups in General Formula (1)can be obtained by using at least one kind of pyrrole compounds shown byGeneral Formulae (30) to (33) written below and at least one kind ofaldehyde compounds shown by General Formulae (34) to (37) written below,and making them react with heat with an acid such as propionic acidexisted in an solvent or not in an solvent.

[In the formulae, R¹²⁹ to R¹³⁶ each mean the same as R¹ to R⁸ of Formula(1) respectively, and R¹³⁷ to R¹⁴⁰ each mean the same as thesubstituents substituting the methine groups, which are X¹ to X⁴ ofFormula (1).]

Further, as another method, metal-free porphyrin compounds whose n is 0,and all of whose X¹ to X⁴ are substituted or unsubstituted methinegroups in General Formula (1) can be obtained by usingdipyromethanedialdehyde compounds of Formula (38) written below anddipyromethane compounds of Formula (39) written below, and making themreact with heat with an acid such as propionic acid existed, in ansolvent or not in an solvent.

[In the formulae, R¹⁴², R¹⁴³, R¹⁴⁵, R¹⁴⁶, R¹⁴⁸, R¹⁴⁹, R¹⁵¹ and R¹⁵² eachmean the same as R¹ to R⁸ of Formula (1) respectively, and R¹⁴¹ and R¹⁴⁷mean the same as the substituents in the methine groups, which are X¹ toX⁴ of Formula (1), respectively.]

As regards azaporphyrin-based compounds shown by General Formula (1) ofthe present invention, whose n is 1 can be obtained by making compoundsshown by both General Formulae (40) and (41) written below, which areobtained by the above-mentioned production methods, or compounds shownonly by General Formula (40) react with heat in some cases, with anorganic metallic salt such as acetylacetonato salt, acetate,trifluoroacetate, etc. of a trivalent or tetravalent metal atom or ahydrate thereof, with an inorganic metallic salt such as halide,sulfate, nitrate, perchlorate, chlorate, hypochlorite, etc. of a metalatom, or a hydrate thereof, or with an disubstituted amide salt such asdimethylamide salt or diethylamide salt, etc., in a solvent of analcohol such as pentanol, hexanol, etc. or of an aromatic solvent suchas benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene,1,2,4-trichlorobenzene, etc.

[In the formulae, R¹ to R¹⁶ and X¹ to X⁴ represent the same groups as R¹to R¹⁶ and X¹ to X⁴ of Formula (1) respectively.]

Alternatively, instead of General Formula (40) the above compound can beobtained by using compounds shown by General formula (42) written below,which are lithium salts, or substituting the compounds with whichoxygen-containing hydrocarbon compounds such as dimethoxyethanecoordinate for the compounds of General Formula (42); or by usingcompounds shown by General Formula (43) written below, which are lithiumsalts, instead of General Formula (41), or substituting the compoundswith which oxygen-containing hydrocarbon compounds such asdimethoxyethane coordinate for the compounds of General Formula (43);and making them similarly react.

[In the formulae, R¹ to R¹⁶ and X¹ to X⁸ represent the same groups as R¹to R¹⁶ and X¹ to x⁸ of Formula (1) respectively.]

Further, compounds of General Formula (45) written below whose centralmetals are tetravalent metals, which are the compounds of the presentinvention, can be obtained by making an oxidizing agent such asdichlorodicyanobenzoquinone, chloranil, etc. work on compounds ofGeneral Formula (44) written below whose central metals are trivalentmetals and hydrogen atoms, which are the compounds of the presentinvention, and by making them react with heat in some cases, in ahalogenated solvent such as dichloromethane, chloroform, dichloroethaneor trichloroethane.

[In the formulae, R¹⁵³ to R¹⁸⁴ represent the same groups as R¹ to R¹⁶ ofFormula (2) respectively, M represents a trivalent metal atom, M⁶represents a tetravalent metal atom, and X⁹ to X²⁴ mean the same as X¹to X⁸ of Formula (1) respectively.]

Further, compounds of General Formula (47) written below, which are thecompounds of the present invention, can be obtained by making compoundsof General Formula (46) written below react with heat in some cases,with lithium compounds of the above-mentioned General Formula (42) or(43), using a silver compound such as trifluoro silver acetate, etc. asa reaction auxiliary agent, in an aromatic solvent such as benzene,toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene,1,2,4-trichlorobenzene, etc.

[In the formulae, R¹⁸⁵ to R²⁰⁸ represent the same groups as R¹ to R¹⁶ ofFormula (1) respectively, M⁷ and M⁸ represent tetravalent metal atoms,Q¹ and Q² represent halogen atoms such as fluorine atom, chlorine atom,bromine atom and iodine atom, and X⁹ to X²⁴ mean the same as X¹ to X⁸ ofFormula (1).]

Further, regarding ones among R¹ to R¹⁶ in which arbitrarily selectedsubstituents are hydrogen atoms, compounds of General Formula (1) inwhich hydrogen atoms are substituted can be obtained by substituting theselected hydrogen atoms for arbitrary substituents, according to aprescribed synthesizing method such as nitration, halogenation,formylation, amination, carboxylation, hydroxylation, acylation,elimination reaction, etc., for example, and using a prescribedsynthesizing method such as reduction, oxidation, isomerization,transition, etc., if necessary.

It should be noted that substituents and the like are shown according toGeneral Formula (1); General Formulae (2) to (4) are included in GeneralFormula (1), so that corresponding substituents and the like canobviously be changed. Dye in the recording layer constituting theoptical recording medium of the present invention is substantially madeof one or more kinds of azaannulene compounds, particularly thecompounds in General Formula (1) to (4), and further, may be mixed withother dye compounds than the above, having the absorption maximumbetween 290 nm and 690 nm in wavelength and high refractive indexbetween 300 nm to 900 nm in wavelength, if necessary. Specifically,cyanine-based compound, squarylium-based compound, naphthoquinone-basedcompound, anthraquinone-based compound, tetrapyraporphyrazine-basedcompound, indophenol-based compound, pyrylium-based compound,thiopyrylium-based compound, azulenium-based compound,triphenylmethane-based compound, xanthene-based compound,indanthrene-based compound, indigo-based compound, thioindigo-basedcompound, merocyanine-based compound, thiazine-based compound,acridine-based compound, oxazine-based compound, dipyromethene-basedcompound, oxazole-based compound, and the like can be mentioned, and aplurality of the compounds may be mixed together. The mixture ratio ofthese compounds is between 0.1 mass % and 30 mass % or so.

When the recording layer is deposited, compounds such as quenchers,compound pyrolysis accelerators, ultraviolet absorbers, adhesives,endoergic or endoergic degrading compounds, or compounds ofsolubility-improving agents can be applied to compounds shown by GeneralFormula (1) as substituents, so as to be efficiect in recording,reproduction and erasure, or so as not to impair recording, reproductionor erasure, and preferably to be less than 3000 in molecular weight.

As specific examples of the quenchers, metal complexes such as:acetylacetonato-based; bisdithiol-based such asbisdithio-,,-diketone-based and bisphenyldithiol-based;thiocatechonal-based; salicylaldehyde oxime-based; andthiobisphenolate-based are favorable. In addition, amine-based metalcomplexes are also favorable.

The compound pyrolysis accelerators are not particularly limited as longas acceleration in pyrolysis of compounds is confirmed bythermogravimetric analysis (TG analysis), etc., and metallic compoundssuch as metal-based anti-knocking agents, metallocene compounds andacetylacetonato-based metal complexes can be mentioned, for example. Asexamples of the metal-based anti-knocking agents, lead-based compoundssuch as tetraethyl lead, etc., and Mn-based compounds such ascymantren[Mn(C₅H₅) (CO)₃], etc. can be mentioned, and as examples of themetallocene compounds, ironbiscyclopentadienyl complex (ferrocene) andbiscyclopentadienyl complexes of Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr,Lu, Ta, W, Os, Ir, Sc and Y can be mentioned. Partivularly, ferrocene,ruthenocene, osmocene, nickelocene, titanocene and derivatives thereofhave the favourable effectiveness of acceleration in pyrolysis.

In addition, other than metallocene, organic acid metallic compoundssuch as iron formate, iron oxalate, iron laurate, iron naphthenate, ironstearate, iron acetate, etc.; chelate iron complexes such asacetylacetonato iron complex, phenanthroline iron complex, bispyridineiron complex, ethylenediamine iron complex, ethylenediaminetetraaceticacid iron complex, diethylenetriamine iron complex,diethyleneglycoldimethylether iron complex, diphosphino iron complex,dimethylglyoxymato iron complex, etc.; iron complexes such as carbonyliron complex, cyano iron complex, ammine iron complex, etc.; halogenatedirons such as ferrous chloride, ferric chloride, ferrous bromide, ferricbromide, etc.; inorganic iron salts such as iron nitrate, iron sulfate,etc.; and further, iron oxide, etc. can be mentioned as iron-basedmetallic compounds. Hereupon, pyrolysis accelerators capable of beingdissolved in organic solvents and of heat, humidity and light-resistingare preferable.

As regards the endoergic or endoergic degrading compounds, compoundsdescribed in Japanese published patent application No. H10-291366 orcompounds having substituents, etc. described in the application can bementioned.

As regards each of the above-mentioned quenchers, compound pyrolysisaccelerators, and endoergic or endoergic degrading compounds, one kindor a mixture of two kinds or more may be used, as need arises.

Alternatively, compounds having quenching ability, compound pyrolysisaccelerating ability, ultraviolet-absorbing ability and adhesive abilitycan be applied as substituents to the azaannulene compounds described inthe present invention, particularly the compounds shown by GeneralFormula (1).

Specifically, a compound residue having quenching ability, compoundpyrolysis accelerating ability, ultraviolet-absorbing ability, adhesiveability, and endoergic or endoergic degrading ability may bond with anazaannulene compound residue of General Formula (1) described in thepresent invention by at least one single bond, double bond or triplebond so that one molecule forms. Preferably, a substituent shown byGeneral Formula (48), which is each substituent of an azaannulene ringof General Formula (1),

[In the formula, L^(n) represents a portion connected to an azaannulenecompound of Formula (1), that is, a single bond, or an atom chain of 1to 20 in carbon number made by and joining at least one kind selectedfrom methylene group, methine group, amino group, imino group, oxygenatom and sulfur atom which may be substituted, and J^(n) represents acompound residue containing a quencher, a compound pyrolysisaccelerater, an ultraviolet absorber, adhesive ability, and endoergic orendoergic degrading ability, which corresponds to R¹ to R¹⁶.]or a substituent shown by General Formula (49), which is a substituentmade by bonding each substituent of an azaannulene ring of GeneralFormula (1) with another substituent

(In the formula, L^(m1) and L^(m2) are next to each other, and also eachrepresent a portion connected to an azaporphyrin-based compound ofFormula (2), that is, a single bond or an atom chain of 1 to 20 incarbon number made by joining at least one kind selected from methylenegroup, methine group, amino group, imino group, oxygen atom and sulfuratom which may be substituted, and J^(m) represents a compound residuecontaining a quencher, a compound pyrolysis accelerater, an ultravioletabsorber, adhesive ability, and endoergic or endoergic degradingability, which corresponds to R¹ to R²².]can be mentioned.

As favorable examples of the atom chains used for L^(n), L^(m1) andL^(m2), single bond, methylene group, imino group, thia group,—C(═O)—OCH₂—, —C(═O)—OCH(CH₃)—, —OCH₂—, —OCH(CH₃)—, —CH₂OCH₂—,—CH₂OCH(CH₃)—, —CH(CH₃)OCH(CH₃)—, —O—C(═O)—, —CH═CH—, —CH═N—, —C(═O)—,—CH═CH—C(═O)O—, —C(C═O)CH₂CH₂C(═O)—O—, the groups made by substitutingthese groups by the above-mentioned substituents, and the like can bementioned.

As favorable examples of J^(n) and J^(m), metallocene residues such asferrocene residue, cobaltcene residue, nickelocene residue, ruthenoceneresidue, osmocene residue and titanocene residue can be mentioned.

As favorable framework examples of General Formula (48), the followingmetal complex residues can be mentioned.

(M′ represents Fe, Ru, Co, Ni, Os or M″Z′₂ (M″ represents Ti, Zr, Hf,Nb, Mo and V, and Z′ represents CO, F, Cl, Br, I, or alkyl groups,alkoxy groups, aryl groups, aryloxy groups, aralkyl groups andaralkyloxy groups of 1 to 10 in carbon number containing substituentssimilar to the above-described R¹ to R¹⁶.).)

Further, as favorable framework examples of General Formula (49), thefollowing metal complex residues can be mentioned.

(M′ represents Fe, Ru, Co, Ni, Os or M″Z′₂ (M″ represents Ti, Zr, Hf,Nb, Mo and V, and Z′ represents CO, F, Cl, Br, I, or alkyl groups,alkoxy groups, aryl groups, aryloxy groups, aralkyl groups andaralkyloxy groups of 1 to 10 in carbon number containing substituentssimilar to the above-described R¹ to R¹⁶.).)

As regards the above-mentioned compound groups, the refractive indexn≧1.9 can be realized in the vicinity of wavelength λ=400 nm, forexample. As regards phthalocyanine-based, azaporphyrin-based orporphyrin-based dye in particular, usually there is a soret band in therange of an ultraviolet ray of 400 nm or less, and there is anabsorption band including a definit maximum value represented by a Qband or the like within 400 nm from this soret band on the longwavelength side. The absorption coefficient k and the refractive index nat the foot of this soret band are adjusted so that the aforementionedconditions are satisfied at the recording wavelengths.

Various kinds of substituent modification may be performed on a parentnucleus of a base molecule of an organic dye selected as describedabove, thereby optimizing a light-absorbing spectrum and improvingworkability such as resolvability of dye. These materials can bedeposited usually by dissolving or dispersing them in an appropriatesolvent, and coating and drying them using a spin coat method, spraymethod and the like. Also, in order to execute high density recording asmuch as possible, a vacuum evaporation method or the like is appliedwith respect to recording (land and groove recording) on both betwengrooves (land portion) and within grooves (groove portion) of guidegrooves formed in a substrate or light-transmissive layer, due to thenecessity to uniformly control the thickness of a dye film for both thegrooves and lands. It is preferable that the thickness of a recordinglayer be within the range of 20 to 200 nm, more preferably in the rangeof 20 to 120 nm. In order to restrain thermal interference and makerecording density high, it is desirable to retain the high refractiveindex of the organic dye recording film and make the film thin.

As shown in the above described FIGS. 1 and 2, a reflective layer can beprovided at a portion adjacent to the recording layer according to theoptical recording medium of the present invention. As materials uesd forthe reflective layer, metals such as gold, silver, aluminum, platinumand copper, and alloys containing those metals can be mentioned. In thecase where blue-violet laser light of 390 to 430 nm in wavelength isused, silver, aluminum and alloys containing them are desirable in termsof cost and optical characteristics, and in particular alloy-basedmaterial composed of highly durable silver and Ti, Pd, Cu, and the likeare desirable. The thickness of the reflective layer is usually within20 to 120 nm, preferably within 10 to 80 nm. Further, instead of theabove-described metal reflective layer a dielectric reflective film inwhich a low refractive index dielectric film and a high refractive indexdielectric film are laminated alternately can be formed. For example, inthe case where the reflectance of the disc is set relatively low, simplestructures such as a two-layer laminated film consisting of aone-quarter wavelength film of SiO₂ (n=1.46) and a one-quarterwavelength film of N₄ (n=2.0) can be employed. It is also possible toadopt film structure of a disc, in which no metal thin layer is used. Asa method for forming the reflective layer, a vacuum evaporation method,sputtering method, ion beam sputtering method or the like can be used.

As regards the structure shown in FIG. 1, a protective film 4 is formedby spin coating organic materials such as ultraviolet curing resin andheat-hardening resin on the reflective layer 3. Further, as shown inFIG. 1, it is also possible to stick a dummy substrate on the protectivefilm in the same manner as conventional DVDs.

Further, regarding the structure shown in FIG. 3, a reflective layer 2and a recording layer 3 are sequentially formed on a substrate 1 whereguide grooves etc. are formed, and after coating the recording layer 3with ultraviolet curing resin, a light-transmissive layer 8 is formed byhardening the resin with UV irradiation. Alternatively, it is alsopossible to separately form the light-transmissive layer 8 beforehand ina film shape with an uniform thickness, and then stick the film throughan adhesion layer such as ultraviolet curing resin or pressure-sensitiveadhesive.

Forming a transparent protective layer between a substrate and arecording layer is efficient with respect to restraining deformation ofthe substrate, which is caused by heat generated at the time ofrecording. Further, in the case where the protective layer is formed ona recording layer 3 through a light-transmissive layer 8 and adhesive asshown in FIG. 3, forming a transparent protective film 4 between organicdye and those layers is also efficient in order to restrain theabove-described deformation of a substrate and to avoid dissolution ofthe organic dye into ultraviolet curing resin. This transparentprotective layer 4 can be formed of a material of a substance or amalgamof an oxide, nitride, sulfide or fluoride of metal (for example Mg, Al,Ti, Zn, Ga, Zr, In, Sn, Sb, Ba, Hf, Ta, Sc, Y or rare-earth element) ormetalloid (Si, Ge).

The vacuum evaporation method, the sputtering method, the ion beamsputtering method, etc. can be used for the formation of thesetransparent protective films. Further, regarding an optical recordingmedium of this structure, a polycarbonate sheet of 10 to 177 μm inthickness made by an injection molding or a cast method, where guidegrooves are formed by thermal transfer using a stamper, is used as alight-transmissive layer, for example. A recording layer made of organicdye and a reflective layer may be deposited in this order on the sheet,and further, a substrate may be stuck to them.

Also, by forming the above-described transparent protective layers onboth sides adjacent to a recording layer, deformation of a substrate,reflective layer, protective film and light-transmissive layer, causedby heat generated at the time of recording, can be restrained morecompletely, and repetitively rewriting characteristics can be improved.

In order to retain the initial reflectances and signal modulationdegrees conforming to each of the standards of CD, DVD, DVR or the like,the thicknesses of the above-described recording film, reflective filmand transparent protective film are optimized by using materials, whichhave appropriate optical constants in the recording laser wavelength,for the recording film, reflective film and transparent protective filmand by calculating the reflectance of a multi-layer film structureconsidering the effectiveness of optical multiple reflection.

The optical recording medium according to the present invention has astructure in which at least one kind of thin film is laminated, asdescribed above, so that it is important to set the thickness of eachlayer such that by actively utilizing multiple interference of light,the initial reflectance is within the range defined by each standard,and the detected modulation degree of the information signal becomes themaximum. Therefore, we are to describe this multiple interference effectof light, particularly the reflectance calculation method; and effectiveFresnel coefficient method.

When r₁ and r₂ are the Fresnel coefficients in media no and n₁, andmedia n₁ and n₂ in FIG. 4 respectively; if the incident angle of thelaser beam is given 0, the amplitude reflectance of a single-tier filmis given by $\begin{matrix}\left\lbrack {{Formula}\quad 1} \right\rbrack & \quad \\{r = {r_{1} + {t_{1}r_{2}t_{1}^{\prime}\quad{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{1}}} + {t_{1}{r_{2}\left( {r_{1}^{\prime}r_{2}} \right)}\quad t_{1}^{\prime}\quad{\mathbb{e}}^{{- 4}\quad{\mathbb{i}}\quad\delta_{1}}} + {t_{1}{r_{2}\left( {r_{1}^{\prime}r_{2}} \right)}^{2}\quad t_{1}^{\prime}\quad{\mathbb{e}}^{{- 6}\quad{\mathbb{i}}\quad\delta_{1}}} + \cdots}} & (1)\end{matrix}$

Herein, $\begin{matrix}\left\lbrack {{Formula}\quad 2} \right\rbrack & \quad \\{\delta_{1} = {\frac{2\quad\pi}{\lambda}n_{1}\quad d\quad\cos\quad\theta_{1}}} & (2)\end{matrix}$

is provided, and the phase difference between a reflecting wave and apassing wave next to each other is 2δ₁. Stokes' law says according tothe Fresnel coefficient in the forward direction and the Fresnelcoefficient (shown with a prime) in the backward direction, therelationship of $\begin{matrix}\left\lbrack {{Formula}\quad 3} \right\rbrack & \quad \\\begin{matrix}{{t_{1}^{\prime} = t_{1}},} & {{r_{1}^{\prime} = {- r_{1}}},} & {{{t_{1}t_{1}^{\prime}} + r_{1}^{2}} = 1}\end{matrix} & (3)\end{matrix}$is established. Therefore, $\begin{matrix}\left\lbrack {{Formula}\quad 4} \right\rbrack & \quad \\{r = \frac{r_{1} + {r_{2}{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{1}}}}{1 + {r_{1}r_{2}\quad{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{1}}}}} & (4)\end{matrix}$can be shown.

In order to obtain the reflectance of a multi-tier film, multipleinterference is calculated as described above using the Fresnelcoefficients on two interfaces of the front and back in the final layerL, and regarding the interface as a hypothetical boundary, and makingR_(L) at the time the effective Fresnel coefficient, calculations areexecuted one after another toward upper layers. Specifically,$\begin{matrix}\left\lbrack {{Formula}\quad 5} \right\rbrack & \quad \\{{\overset{\sim}{R}}_{L} = r_{L + 1}} & (5)\end{matrix}$is given, and according to the above-described calculation method inwhich the final layer is a single-layer film, the complex reflectance inthe final layer is $\begin{matrix}\left\lbrack {{Formula}\quad 6} \right\rbrack & \quad \\{{\overset{\sim}{R}}_{L - 1} = \frac{r_{L} + {{\overset{\sim}{R}}_{L}\quad{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{L}}}}{1 + {r_{L}{\overset{\sim}{R}}_{L}\quad{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{L}}}}} & (6)\end{matrix}$

With respect to the other layers calculation can similarly be performed,and regarding a j layer $\begin{matrix}\left\lbrack {{Formula}\quad 7} \right\rbrack & \quad \\{{\overset{\sim}{R}}_{j - 1} = \frac{r_{j} + {\overset{\sim}{R}j\quad{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{j}}}}{1 + {r_{j}{\overset{\sim}{R}}_{j}\quad{\mathbb{e}}^{{- 2}\quad{\mathbb{i}}\quad\delta_{j}}}}} & (7)\end{matrix}$is calculated. So that by calculating from the final layer to the firstlayer in order, the reflectance in a multi-tier film can be calculated.

For example, regarding an optical recording medium shown in FIG. 3 inwhich a polycarbonate substitute 1, a silver reflective film 2 of 15 nmin thickness, an organic dye recording film 3 of (n, k)=(1.95, 0.15)(the film thickness is a variable parameter), an SiO₂ protective film 4of 30 nm in thickness and a light-transmissive layer 8 of polycarbonatehave been formed in order, a calculation example of the reflectance whenrecording and reproduction are executed from the light-transmissivelayer side is shown in FIG. 5. For example, if the thickness of theorganic dye recording film 3 is 80 nm, when the initial reflectancebefore recording is 15% and refractive index of the organic dye filmafter recording is n=1.7, the reflectance thereof is 8%, so that thethickness of an organic dye film of a low reflectance type mediumstructure, suitable for High-to-Low recording of modulationdegree=(initial reflectance−reflectance after recording)/initialreflectance=47% is thus ditermined. Although in the case of the highreflectance type, the thickness of the silver reflective film becomesgreater and in the case where Low-to-High recording is performed, thefilm structure is different, optimization is possible by the similarcalculation method.

In the present invention, the explanation has been given with respect tothe rewritable type; however the present invention can be applied to thewrite-once type optical recording media capable of recording only once,because unless erasure is executed, the recording and reproducing methodand the structure thereof are not different from those of the write-oncetype media. Therefore, high compatibility can be retained with theconventional media.

Hereinafter, the present invention will be described referring toembodiments, however the present invention is not limited to thoseembodiments.

Embodiment 1

This embodiment is an example of a DVD using blue laser of wavelengthλ=405 nm.

A polycarbonate substrate the dimensions of which are 0.6 mm inthickness and 120 mm in outer diameter has been made from a stamper withgrooves in the shape of 0.6 μm in pitch, 50 nm in groove depth and 0.28μm in groove width by an injection molding method. The film structure ofthis example is the same as that shown in FIG. 1. Tetraazaporphyrin dye<tetara-t-butyl-5,10,15,20-tetraazaporphyrinoxovanadium(IV)> shown asrecording layer 2 by General Formula (A) has been deposited by a vacuumevaporation method on grooves on the substrate so that the film thicnessbecomes 60 nm. The refractive index and the absorption coefficient ofthe recording layer 2 were n=1.8 and k=0.05 at 405 nm, respectively.Subsequently, an optical recording medium of the same outer shape as theDVD has been made by depositing a silver reflective layer 3 of 100 nm inthickness on this recording layer by a sputtering method, thendepositing UV curing resin [SD17] (produced by DAINIPPON-INK ANDCHEMICALS, INCORPORRATED) by a spin coating method on the reflectivelayer 3 in the thickness of approximately 3 μm as a protective film 4,and applying UV adhesive thereover so that a dummy substrate of 0.6 mmin thickness (made of polycarbonate) is stuck. The initial reflectanceof the above disc was 23%.

A simply repetitive signal corresponding to the pit length of 0.5 μm wasrecorded on grooves of the recording medium through the polycarbonatesubstrate under the condition of 405 nm in wavelength, NA=0.65, linearvelocity=3.5 m/s and recording power=8.5 mW, by an optical discevaluation apparatus with blue-violet laser produced by PulstecIndustrial, Co., Ltd. When the recorded portion was reproduced at areproducing power of 0.5 mW, C/N=59 dB was obtained. FIG. 6 shows the RFsignal output of this recording pattern.

After the recording, when the track was erased with continuous (DC)light of an erasing power of 3.7 mW, the amount of the signal whichremained after erasing was C/N=43 dB, and an erasure ratio 15 dB wasobtained. FIG. 7 shows the RF signal output at this time. The remainder,which has not been erased, is slightly observed. Further, whenre-recording was executed on the same track on the same condition as theabove-described recording, C/N=56 dB was obtained. FIG. 8 shows the RFsignal output at this time. After the recording and erasure was repeated20 times on the same track, an evaluation of the rewritingcharacteristics was executed and the same C/N value was obtained.

Embodiment 2

This embodiment is also an example of a DVD using blue laser ofwavelength λ=405 nm.

The same substrate, organic dye recording film, silver reflective filmand protective film were used. The film structure of this example isshown in FIG. 2. The difference between this example and Embodiment 1 isthat SiO₂ of 30 nm in film thickness is deposited by a sputtering methodbetween the substrate 1 and the recording film 3 and between therecording film 3 and the reflective film 5 as a transparent protectivelayer 5 and as a transparent protective layer 6, respectively. Theinitial reflectance of the disc was 12%, which virtually corresponds tothe calculated value.

A simple repetitive signal corresponding to the pit length of 0.5 μm wasrecorded on the same condition as Embodiment 1.

When the recorded portion was reproduced at a reproducing power of 0.5mW, the C/N ratio=59 dB was confirmed. FIG. 9 shows the RF signal outputconcerning this recording pattern.

After the recording, when the track was erased with continuous (DC)light of an erasing power of 3.7 mW, the amount of the signal whichremained after erasing was C/N=19 dB, and an erasure ratio 32 dB wasobtained. FIG. 10 shows the RF signal output at this time, and it isunderstand that erasure was almost completely done. Further, whenrecording was again executed on the same track on the same condition asthe above-described recording, C/N=51 dB was obtained. FIG. 11 shows theRF signal output concerning this recording pattern. When the recordingand erasure was repeated 20 times on the same track and an evaluation ofthe rewriting characteristics was executed, signal deterioration almostdid not occur with C/N kept at 51 dB. As is obvious from FIG. 12, signaldeterioration can hardly be observed. By holding the recording filmbetween hard dielectric materials (SiO₂ in this example), it isconsidered that deformation occurred only in the organic dye recordingfilm, effects on the substrate and the reflective film was restrainedand repetitive rewriting performance was improved. Deformation traces onthe dye layer side, which were detected when observing by SEM anexfoliated interface between the SiO₂ dielectric layer on the substrateside and the dye layer after the recording, after the erasure and afterthe rerecording, are shown in FIGS. 21A to 21C, respectively. Also, aSEM observation image of the interface on the SiO₂ dielectric layer sideafter the recording is shown in FIG. 21D. It is notable that there ishardly observed any deformation trace left on the surface of the SiO₂dielectric layer adjacent to the dye layer, and a dome-shaped cavityonly corresponding to the recorded portion in the dye layer wasdetected. Furthermore, it is directly observed that the dorm-shapeddeformation trace was planarized by erasing using laser. In addition,there was no change happened on the surface of the SiO₂ dielectric layeron the substrate side after erasure and after rerecording.

Embodiment 3

This embodiment is an example of a DVR (an optical disc in whichrecording and reproduction are performed through a light-transmissivelayer of 10 to 177 μm in thickness) using blue laser of wavelength λ=405nm.

An example of a film structure in FIG. 3 concerning a recording mediumcapable of favorably recording and reproducing in an optical system ofwavelength 405 nm and NA=0.85 is shown. Here note that guide grooveswith a track pitch of 0.64 μm are formed in a polycarbonate substrate 1and the width of the guide grooves is set to 50% so that recording canbe done both on lands and grooves. Specifically, the track pitch isvirtually 0.32 μm. Also, the depth of each groove is 40 nm. A silveralloy reflective film 2 of 12 nm in thickness was deposited thereon by asputtering method, and diazaporphyrin dye<2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-diazaporphyrincopper(II)> shown by General Formula (B) written below is used to forman organic dye film 3 by a vacuum evaporation method.

The organic dye film was 75 nm in thickness, and the optical constantthereof was refractive index n=1.9 and k=0.15. As a transparentprotective layer 7, SiO₂ of 30 nm in film thickness was deposited by asputtering method. The purpose of forming this film is to enhence thehardness of the surface and to improve repetitive recordingcharacteristics, however here it may be noted to be used for protectinga recording film. As described above, a light-transmissive layer has athickness of 100 μm. This layer is made by sticking a polycarbonatesheet with pressure-sensitive adhesive (PSA), and the thicknessincluding the above all was set to 100 μm.

The initial reflectance of an optical disc made in this manner was 14%,which is close to the calculated design value. The linear velocity was5.72 m/s for recording, the reproduction light power was 0.3 mW and therecording pattern was a single carrier wave of 0.35 μm in mark length.Also, for recording a single mark, seven pulse lines having the samewidth were made to enter with the pulse/space ratio being 50%, the peakpower was 6.0 mW, and the medium's characteristics were evaluated bymeasuring C/N with RBW=30 kHz by a spectrum analyzer. In the case of theabove-described optical recording medium, a value of 45 dB was obtainedas a result after the above-mentioned recording and reproductionexperiment were executed. FIG. 13 shows the RF signal output concerningthis recording pattern.

After the recording, when the track was erased twice with continuous(DC) light of an erasing power of 3.0 mW, the amount of the signal whichremained after erasing was C/N=10 dB, and an erasure ratio 32 dB wasobtained. FIG. 14 shows the RF signal output at that time. Further, whenrerecording was executed on the same track on the same condition as theabove-described recording, a C/N value of 43 dB was obtained. FIG. 15shows the RF signal output at that time. This recording and erasure wasrepeated 10 times on the same track and the rewriting characteristicswere evaluated, and C/N of 43 dB was obtained without fail.

Also, the C/N value of the disc at the recording by a single carrierwave of 0.173 μm in recording mark length was 42 dB, and the C/N valueat the recording by a single carrier wave of 0.173 μm in recording marklength was 51 dB. Further, when a random pattern recording of a (1, 7)sign of 0.38 μm in the shortest mark length was executed, such an eyepattern as shown in FIG. 16 was obtained.

Embodiment 4

This embodiment is also an example of a DVR (an optical disc in whichrecording and reproduction are performed through a light-transmissivelayer of 10 to 177 μm in thickness) using blue laser of wavelength λ=405nm.

The same polycarbonate substrate as used in Embodiment 3 was used. Thefilm structure in this example is shown in FIG. 17: polycarbonatesubstrate (1)/dielectric film 1 (9)/dielectric film 2 (10)/organic dyerecording film (3)/transparent protective layer (7)/light-transmissivelayer (8).

Si₃N₄ (n=2.0) of 60 nm in film thickness and SiO₂ (n=1.46) of 60 nm infilm thickness were stacked in order on the substrate 1 by a reactivesputtering method in which nitrogen gas and oxygen gas are appropriatelymixed into argon sputter operation gas respectively and a silicon targetwas used as a target. As regards these films, film thicknesses thereofare decided so that an organic dye recording layer is protected anddeformation of recorded marks is prevented from acting on the substrateside, and so that the disc's initial reflectance conforms to thestandard (15% to 25% in the case of the DVR-Blue) as a film structureincluding the later mentioned recording layer and transparent protectivelayer.

Further, monoazaporphyrin dye<2,3,7,8,13,17-hexaethyl-12,18-dimethyl-5-azaporphyrin copper(II)> shownby General Formula (C) written below was deposited as a recording layersuch that its film thickness would be 50 nm by a vacuum evaporationmethod. The refractive index and the absorption coefficient of therecording layer were n=2.1 and k=0.1 at 400 nm. Then, SiO₂ transparentprotective layer of 30 nm in thicknes was deposited on this recordinglayer by a sputtering method. The following is the same as Embodiment 3.

As regards the optical disc produced in this manner, the same value asthe design value by calculation, which is the reflectance ofapproximately 20% with a light source of 405 nm, was obtained by causingmultiple reflection without having a metal reflective film.

The linear velocity was 5.72 m/s for recording, the reproducing lightpower was 0.3 mW and the recording pattern was a single carrier wave of0.35 μm in mark length. Also, for recording a single mark, seven pulselines having the same width were made to enter with the pulse/spaceratio being 50%, the peak power was 5.0 mW, and the medium'scharacteristics were evaluated by measuring C/N with RBW=30 kHz by aspectrum analyzer. In the case of the above-described optical recordingmedium, a value of 48 dB was obtained as a result after theabove-described recording and reproduction experiment was executed.After the recording, when the track was erased with continuous (DC)light of an erasure power of 3.0 mW, the amount of the signal whichremained after erasing was C/N=25 dB, and an erasure ratio 23 dB wasobtained. Further, when rerecording was executed on the same track onthe same condition as the above-described recording, a C/N value of 48dB was obtained. After the recording and erasure was performed 10 timeson the same track, an evaluation of the rewriting characteristics wasexecuted, and although change of 1 dB or less in the C/N value wasslightly noticed in the first three attempts, it was possible to retainC/N of 48 dB in the end.

Embodiment 5

This embodiment is an example of a DVD using red laser of wavelengthλ=658 nm.

The recording medium obtained in Embodiment 1 was used. However,regarding a recording film, tetraazaporphyrin dye was deposited by aspin coating method using ethylcyclohexane solution (20 g/l) on groovesof the substrate such that the film thickness thereof would be 90 nm. Asregards the guide groove of the substrate, the track pitch was 0.74 μm,the width was 0.33 μm and the depth was 150 nm. The refractive index andthe absorption coefficient of the recording layer were n=2.1 and k=0.05,respectively. Subsequently, an optical recording medium of the sameouter shape as the DVD has been made by depositing a SiO₂ transparentprotective layer of 30 nm in thickness on this recording layer by asputtering method, further depositing a silver reflective layer of 100nm in thickness by a sputtering method, then depositing by a spincoating method UV curing resin <Trade Name SD17> (produced by DAINIPPONINK AND CHEMICALS, INCORPORATED) as a protective film on this reflectivelayer such that the thickness thereof becomes approximately 3 μm, andapplying UV adhesive to stick a dummy substrate of 0.6 mm in thickness(made of polycarbonate) thereto. On this occasion, the initialreflectance of the disc was 47%. A simply repetitive signalcorresponding to the pit length of 0.8 μm was recorded on groovesthrough the polycarbonate substrate on the condition of 658 nm inwavelength, NA=0.60, linear velocity=3.5 m/s and recording power=9 mW,by an optical disc evaluation apparatus with red laser produced byPulstec Industrial, Co., Ltd. When the recorded portion was reproducedat a reproducing power of 0.5 mW, C/N=58 dB was obtained.

After the recording, when the track was erased with continuous (DC)light of an erasure power of 4 mW, the amount of the signal whichremained after erasing was C/N=30 dB, and an erasure ratio 28 dB wasobtained. Further, when rerecording was executed on the same track onthe same condition as the above-described recording, C/N=55 dB wasobtained. After the recording and erasure was repeated 20 times on thesame track, an evaluation of the rewriting characteristics was executed,and signal deterioration could hardly be observed.

Embodiment 6

This embodiment is an example of a CD using infrared laser of wavelengthλ=780 nm.

A SiO₂ transparent protective layer of 30 nm in thickness was depositedby a sputtering method on a substrate with guide grooves, each of whosetrack pitch is 0.74 μm, width is 0.33 μm and depth is 170 nm, and thenphthalocyanine dye was deposited by a spin coating method usingethylcyclohexane solution (20 g/l) on the grooves such that the filmthickness thereof would be 100 nm. The refractive index and theabsorption coefficient of the recording layer were n=2.2 and k=0.1,respectively. Further, a silver reflective layer of 100 nm in thicknesswas deposited by a sputtering method, and then UV curing resin <SD17>(produced by DAINIPPON INK AND CHEMICALS, INCORPORATED) as a protectivefilm of 3 μm was deposited by the spin coating method on the reflectivelayer. On this occasion, the initial reflectance of the disc was 68%. Asimply repetitive signal corresponding to the pit length=1.2 μm wasrecorded on grooves through the polycarbonate substrate on the conditionof 781 nm in wavelength, NA=0.50, linear velocity=2.4 m/s and recordingpower=10.5 mW, by an optical disc evaluation apparatus with red laserproduced by Pulstec Industrial, Co., Ltd. When the recorded portion wasreproduced at a reproducing power of 0.7 mW, C/N=57 dB was obtained.FIG. 18 shows the RF signal output at that time.

After the recording, when the track was erased with continuous (DC)light of an erasing power of 3 mW, the amount of the signal whichremained after erasing was C/N=33 dB, and an erasure ratio 24 dB wasobtained. FIG. 19 shows the RF signal output at that time. Further, whenrerecording was executed on the same track on the same condition as theabove-described recording, C/N=54 dB was obtained. FIG. 20 shows the RFsignal output at that time. After the recording and erasure was repeated20 times on the same track, an evaluation of the rewritingcharacteristics was executed, and signal deterioration could hardly beobserved.

As is obvious from the above explanation, according to the presentinvention, laser light of the same wavelength can be used with respectto recording, reproduction and erasure, so that a rewritable opticalinformation recording medium can be provided by a simple recording andreproducing apparatus in which one laser light source, particularly asmall laser diode light in weight is mounted. The conventional CD-RWdrive and DVD-RW drive can be used in particular as recording andreproducing apparatuses of optical recording media of the presentinvention without any change. Further, only by adding erasing functions,the present invention can be applied to the CD-R drive and DVD-R drive.Complicated signal detection such as polarization optical system is notat all needed. Further, recording, reproducing and erasing on differentlaser wavelengths can be performed, so that the present invention can beapplied to a mixed drive of CD and DVD.

The optical recording medium of the present invention is a recordingmedium including the recording layer which is made of a thin organic dyefilm uniformly deposited and changes according to laser irradiation, sothat the noise level is sufficiently low, and the light modulationdegree (contrast), namely the C/N value is high. As regards azaannulenecompounds used in the optical recording medium of the present invention,particularly azaporphyrin groupes and porphyrin groupes such asphthalocyanine-based, naphthalocyanine-based and mono andtetra-azaporphyrin-based, and metal complexes thereof; light-absorbingspectra can be adjusted in accordance with the laser wavelengths used,so that it is possible to provide optical recording media suitable forrecording and reproducing apparatuses using semiconductor lasers of avariety of wavelengths. Particularly, an optical recording medium whichis applied to short wavelength lasers such as ultraviolet andblue-violet lasers can be provided to realize high recording density.

Also, by utilizing optical multiple reflection caused by using adielectric protective film, a reflective film, the reflectances beforeand after a recording can be easily set, and also a recording method canbe freely selected. Both land and groove recording and in-grooverecording can be performed by using substrates with appropriate guidegrooves. Further, both substrate reading and surface reading arepossible. Accordingly, it is possible to provide optical recording mediawhich are perfectly compatible with existing CDs and DVDs,next-generation optical discs (so-called DVR-Blue and DVD-Blue) and thelike, involving the high and low reflectance types, or the High-to-Lowand Low-to-High recordings.

Furthermore, an optical recording medium can be provided, in which thefilm structure is simplified, uniform characteristics and repeatabilityare obtained, and light resistance and weather resistancecharacteristics are high, reliability can be obtained, and theproduction cost is reduced to be inexpensive.

1. A rewritable optical information recording medium, comprising atleast one light-absorbing organic compound film which is substantiallycomposed of only at least one kind of light-absorbing organic compound(including metal complexes thereof) as a recording film, whereinrecording and erasure of information are executed by a reversiblephysical change of the compound film substance caused by laser lightirradiation.
 2. A rewritable optical information recording mediumaccording to claim 1, wherein said physical change is a change in shape.3. A rewritable optical information recording medium according to claim1, wherein data recording is performed by a physical change locallycaused by the irradiation of recording laser light, data reproduction isperformed by detecting change in intensity of returned light ofreproducing laser light having less power than said recording laserlight, and data erasure is performed by applying at least oncecontinuous light or pulse light having more laser power than saidreproducing laser light and less power than said recording laser light.4. A rewritable optical information recording medium according to claim1, wherein said light-absorbing organic compound absorbs at least onekind of light having a wavelength selected from 350 nm to 850 nm inwavelength.
 5. A rewritable optical information recording mediumaccording to claim 1, wherein said light-absorbing organic compound isan organic dye compound of less than 3000 in molecular weight.
 6. Arewritable optical information recording medium according to claim 4,wherein said organic dye compound is selected from at least one kind ofazaannulene compounds (including metal complexes thereof).
 7. Arewritable optical information recording medium according to claim 6,wherein the wavelengths of laser light used for recording, reproductionand erasure are in the range of 350 nm to 450 nm, and said organic dyecompound is an azaannulene compound shown by the following GeneralFormula (1).

[In the formula, R¹ to R¹⁶ each show individually a hydrogen atom, ahalogen atom, a nitro group, a cyano group, a substituted orunsubstituted hydrocarbon radical, a substituted or unsubstitutedhydroxyl group, a substituted or unsubstituted amino group, or asubstituted or unsubstituted mercapto group; X¹ to X⁸ each showindividually a nitrogen atom, or a substituted or unsubstituted methinegroup; substituents in R¹ to R¹⁶ and in methine groups may bond to eachother through a connecting radical; and there may be contained oxygenatoms, substituted or unsubstituted sulfur atoms and substituted orunsubstituted nitrogen atoms between carbon atoms in substituted orunsubstituted hydrocarbon radicals, in hydrocarbon-substituted hydroxylgroups, in hydrocarbon-substituted mercapto groups and/or inhydrocarbon-substituted amino groups. Further, n represents 0 or 1; whenn is 0, M represents a bivalent metal atom which may have ligands, or atrivalent or tetravalent metal or metalloid atom which has a substituentand/or ligand, and when n is 1, M represents a trivalent metal atom andone hydrogen atom, or a tetravalent metal atom.]
 8. A rewritable opticalinformation recording medium according to claim 7, wherein thewavelengths of laser light used for recording, reproduction and erasureare in the range of 350 nm to 450 nm, and said organic dye compound is atetraazaporphyrin compound shown by the following General Formula (2).

[In the formula, R to R²⁴ each show individually a hydrogen atom, ahalogen atom, a nitro group, a cyano group, a substituted orunsubstituted hydrocarbon radical, a substituted or unsubstitutedhydroxy group, a substituted or unsubstituted amino group, or asubstituted or unsubstituted mercapto group; substituents in R¹⁷ to R²⁴may bond to a substituent on a tetraazaporphyrin ring to form aliphaticrings through connecting radicals; and there may be contained oxygenatoms, sulfur atoms and substituted or unsubstituted nitrogen atomsbetween carbon atoms in substituted or unsubstituted hydrocarbonradicals, in hydrocarbon-substituted hydroxyl groups, inhydrocarbon-substituted mercapto groups and/or inhydrocarbon-substituted amino groups. M¹ represents a bivalent metalatom which may have a ligand, or a trivalent or tetravalent metal ormetalloid atom which has a substituent and/or ligand.]
 9. A rewritableoptical information recording medium according to claim 6, wherein thewavelengths of laser light used for recording, reproduction and erasureare in the range of 600 nm to 700 nm, and said organic dye compound isan azaannulene compound shown by the following General Formula (3).

[In the formula, R²⁵ to R⁴⁰ each show individually a hydrogen atom, ahalogen atom, a nitro group, a cyano group, a substituted orunsubstituted hydrocarbon radical, a substituted or unsubstitutedhydroxy group, a substituted or unsubstituted amino group, or asubstituted or unsubstituted mercapto group; X⁹ to X¹⁶ each showindividually a nitrogen atom, or a substituted or unsubstituted methinegroup containing one of the groups or atoms shown by R¹ to R¹⁶;substituents in R²⁵ to R⁴⁰ and in methine groups may bond to each otherto form aliphatic rings through connecting radicals; and there may becontained oxygen atoms, substituted or unsubstituted sulfur atoms andsubstituted or unsubstituted nitrogen atoms between carbon atoms insubstituted or unsubstituted hydrocarbon radicals, inhydrocarbon-substituted hydroxyl groups, in hydrocarbon-substitutedmercapto groups and/or in hydrocarbon-substituted amino groups. Further,n represents 0 or 1; when n is 0, M² represents a bivalent metal atomwhich may have ligands, or a trivalent or tetravalent metal or metalloidatom which has a substituent and/or ligand, and when n is 1, M²represents a trivalent metal atom and one hydrogen atom, or atetravalent metal atom.]
 10. A rewritable optical information recordingmedium according to claim 6, wherein the wavelengths of laser light usedfor recording, reproduction and erasure are in the range of 600 nm to700 nm, and said organic dye compound is a tetraazaporphyrin compoundshown by General Formula (2).
 11. A rewritable optical informationrecording medium according to claim 6, wherein the wavelengths of laserlight used for recording, reproduction and erasure are in the range of750 nm to 850 nm, and said organic dye compound is a phthalocyaninecompound shown by the following General Formula (4).

[In the formula, R⁴¹ to R⁷² each show individually a hydrogen atom, ahalogen atom, a nitro group, a cyano group, a substituted orunsubstituted hydrocarbon radical, a substituted or unsubstitutedhydroxy group, a substituted or unsubstituted amino group, or asubstituted or unsubstituted mercapto group; substituents in R⁴¹ to R⁷²and in methine groups may bond to each other through connectingradicals; and there may be contained oxygen atoms, sulfur atoms andsubstituted or unsubstituted nitrogen atoms between carbon atoms insubstituted or unsubstituted hydrocarbon radicals, inhydrocarbon-substituted hydroxyl groups, in hydrocarbon-substitutedmercapto groups and/or in hydrocarbon-substituted amino groups. nrepresents 0 or 1; when n is 0, M³ represents a bivalent metal atomwhich may have ligands, or a trivalent or tetravalent metal or metalloidatom which has a substituent and/or ligand, and when n is 1, M³represents a trivalent metal atom and one hydrogen atom, or atetravalent metal atom.]
 12. A rewritable optical information recordingmedium according to claim 1 further comprising: a transparent protectivelayer between said light-absorbing organic compound recording film and asubstrate, or adjacently on the side or on the both sides of saidlight-absorbing organic compound recording film.
 13. A rewritableoptical information recording medium according to claim 12, wherein saidtransparent protective layer is composed of at least one kind selectedfrom inorganic sulfide, inorganic oxide and inorganic nitride.
 14. Arecording and reproduing method, wherein a rewritable opticalinformation recording medium including at least one light-absorbingorganic compound film substantially composed of only at least one kindof light-absorbing organic compounds as a recording film is used, andthe recording and erasure of information are performed by a reversiblephysical change of said light-absorbing organic compound film substancecaused by laser light irradiation.
 15. A recording and reproduing methodaccording to claim 14, wherein with respect to a rewritable opticalinformation recording medium including at least one light-absorbingorganic compound film substantially composed of only at least one kindof light-absorbing organic compounds, data recording is performed bylocally causing a physical change in said organic dye film substancewith the irradiation of recording laser light, data reproduction isperformed by detecting change in intensity of returned light ofreproducing laser light having less power than said recording laserlight, and data erasure is performed by applying at least oncecontinuous light or pulse light having laser power more than saidreproducing laser light and less than said recording laser light toreverse said physical change.
 16. A recording and reproduing methodaccording to claim 14, wherein said physical change is a change inshape.
 17. A recording and reproducing apparatus, comprising arewritable optical information recording medium which has at least onelight-absorbing organic compound film as a recording film substantiallycomposed of only at least one kind of light-absorbing organic compounds,wherein the recording and erasure of information are performed by areversible physical change of said light-absorbing organic compound filmsubstance caused by laser light irradiation.